Solution Manual For Chemistry The Science in Context 5th Edition Thomas R Gilbert Rein V Kirss Natalie Foster Stacey Lowery Bretz Geoffrey Davies

Solution Manual for Chemistry The Science in
Context, 5th edition, Thomas R Gilbert, Rein V Kirss,

Natalie Foster, Stacey Lowery Bretz, Geoffrey Davies
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Solution Manual for Chemistry The Science in Context, 5th edition, Thomas R Gilbert, Rein V
CHAPTER 13 | Chemical Kinetics: Reactions in the Atmosphere
13.1. Collect and Organize

For the plot of Figure P13.1, we are to identify which curves represent [N2O] and [O2] over time for the
conversion of N2O to N2 and O2 according to the equation
2 N2O(g) → 2 N2(g) + O2(g)
Analyze
As the reaction proceeds, the concentration of the reactant, N 2O, decreases and the concentration of the
product, O2, increases. The rate at which N2O is used up in the reaction is twice the rate at which O 2 is
produced.
Solve
The [N2O] is represented by the green line and [O2] is represented by the red line.
Think About It
Notice that [N2], represented by the blue line, increases twice as fast as [O 2] because there are two N2
molecules produced for every O2 molecule in the reaction.

For the plot of Figure P13.2, we are to identify which curves represent [SO2] and [O2] over time for the
reaction of SO2 with O2 to form SO3 according to the equation
SO2 ( g ) + 12 O2 ( g ) → SO3 ( g )
Analyze
As the reaction proceeds, the concentrations of the reactants, SO2 and O2, decrease over time. The rate at
which SO2 decreases in the reaction is twice the rate at which O2 is used up based on the balanced equation.
Solve
The blue line represents [SO2] and the green line represents [O2].
Think About It
Because one molecule of SO3 is produced for every molecule of SO2 reacted, [SO3] (red line) increases at
the same rate at which [SO2] decreases.

For three different initial concentrations of reactant A shown in Figure P13.3, we are to choose which
would have the fastest rate for the conversion 2 A → B.
Analyze
We are given that the reaction is second order in A. The rate law is written as follows:
Rate = k[A]2
As the concentration of A increases, the rate increases.
57
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58 | Chapter 13
Solve
(b) has the fastest reaction rate because it has the highest concentration of A.
Think About It
The higher the concentration of reactant molecules, the more often they collide, which increases the rate of
the reaction.

Knowing that the rate of the reaction
A+B→C
is first order in both A and B, we are to choose the sample in Figure P13.4 that produces the fastest initial
rate.
Analyze
The initial rate of a reaction depends on the concentration of the reactants involved in the rate law expression.
For the reaction described in this problem, the rate law would be
Rate = k[A][B]
Therefore, the higher the concentrations of both A and B, the faster the rate of the reaction.
Solve
(c) has the highest concentration of A (seven red spheres) and B (six blue spheres), compared to (a) with
four A and five B and (b) with six A and five B, so (c) has the fastest initial rate.
Think About It
The lower the concentration of the reactants, the slower the initial rate of the reaction. In this problem, (a)
would give the slowest initial rate.

By examining the four reaction profiles depicted in Figure P13.5, we must identify which reaction has the
greatest initial rate.
Analyze
In all of the reactions depicted, the concentration of reactants decreases as a function of time. The reaction
with the greatest initial rate will exhibit the greatest decrease in concentration of reactants at the start of the
reaction. This will also correspond to the line with the greatest (most negative) slope.
Solve
The black line (d) has the greatest initial change in the concentration of reactants, and so, the greatest initial
rate.
Think About It
(d) represents a reaction that also ends up with the lowest concentration of reactants over the time period
shown. This is not always the case for the reaction with the fastest initial rate; other reactions may start out
more slowly but proceed further over a period of time.

Chemical Kinetics: Reactions in the Atmosphere | 59
For the three reaction profiles in Figure P13.6, we are to indicate which one has the slowest and which has
the fastest reaction rate.
Analyze
The activation energy is the energy barrier that the reactants must overcome in order to form products; the
lower the activation energy barrier, the faster the reaction. The rate of a reaction is determined by
the activation energy (Ea) of the slowest step. All of the reactions shown consist of a single step. The Ea is
the energy difference between the reactants (on the left side of the graph) and the transition state (the
highest point on the reaction profile curve).
Solve
(a) Reaction profile (a) has the largest Ea and therefore is the slowest reaction.
(b) Reaction profile (b) has the lowest Ea and therefore is the fastest reaction.
Think About It
Be careful not to assume that reaction (c) is slow because it is nonspontaneous. The rate of a reaction does
not depend on the thermodynamics of the reactants and the products.

We are to match the reaction profile in Figure P13.7 with the one of the reactions given.
Analyze
The reaction profile shows a two-step reaction that has a slightly larger activation energy for its second step
than its first step.
Solve
(c) is correct because the graph describes a two-step reaction with the first step faster than the second.
Think About It
Reaction (b), which occurs in a single step, would show only one transition state and one activation energy
in its reaction profile.

We are to choose the mechanism that is consistent with the reaction profile in Figure P13.8, showing two
activation energies.
Analyze
The presence of two activation energies in the reaction profile means that there are two steps in the
mechanism. The relative activation energies of the two steps tell us the relative rates of the two steps, with
the step having the smaller Ea being the fastest.
Solve
(a) is consistent with the reaction profile because there are two transition states shown and the activation
energy of the second step is lower than that of the first step, so the second step proceeds at a faster rate than
the first step.
Think About It
A single-step reaction as in (b) would give a reaction profile showing only a single transition state and one
activation energy barrier.
60 | Chapter 13

Given the reaction profile of an uncatalyzed reaction (Figure P13.9), we are to identify the transition state
(activated complex), the activation energy in the forward and reverse direction, and the overall energy
change for the reaction depicted.
Analyze
A transition state is the highest-energy arrangement of atoms in a transformation. The activation energy of
a reaction in the forward direction is the difference between the energy of the reactants and the transition
state, while the activation energy of a reaction in the reverse direction is the difference between the energy
of the products and the transition state. The overall change in energy for the reaction is the difference in
energy between the reactants and products.
Solve
(a) The transition state is 3*.
(b) The activation energy of the reaction in the forward direction is a, the red arrow.
(c) The activation energy of the reaction in the reverse direction is b, the black arrow.
(d) The change in energy for the reaction is c, the blue arrow.
Think About It
Notice that the blue arrow, c, points down in this case. Since the products are lower in energy than the
reactants in this transformation, the reaction is exothermic and energy is released.

We are asked to identify the energy difference between the reactants and products, as well as the activation
energy for the forward and reverse reactions, depicted in Figure P13.10.
Analyze
The activation energy (Ea) for a reaction is the difference in energy between the starting materials (reactants
for the forward reaction, products for the reverse reaction) and the transition state. The difference in energy
between the reactants and products corresponds to the energy change for the reaction.
Solve
(a) Ea in the forward direction is b.
(b) Ea in the reverse direction is a.
(c) The change in energy for the reaction is c.
Think About It
The change in energy for a reaction is a thermodynamic property and is not influenced by the rate of the
reaction.

We are asked to predict how the curves of a plot of [NO], [NO 2], [O3], and [VOC] versus time would be
different on a cloudy day than they are on a sunny day, as shown in Figure P13.11.
Analyze
On a cloudy day, less sunlight will be present, altering the concentration of some species. NO2 is formed
from the oxidation of NO in the presence O2. O3 is formed by the decomposition of NO 2 in the presence of
sunlight. The other product of the decomposition of NO 2 is an oxygen radical O, which is required for the
formation of O3. VOCs and NO form in vehicle exhaust in the absence of sunlight.
Solve
In the absence of sufficient sunlight, NO2 will be formed from NO (generated by vehicles), but will not be
broken down, so [NO2] will increase over time, while [NO] will slowly decrease. The absence of sunlight
will also ensure that [O3] stays low over most of the day. VOCs will be formed throughout the day but not
broken down by sunlight, meaning [VOC] will continue to rise over the day.
Think About It
Smog will still form, though [NO2] will rise later in the day.

Using the equations or atmospheric maps depicted in Figure P13.12, we are to answer questions about
reactions that take place in our atmosphere. Equations may represent overall reactions, or elementary steps
in a reaction. The color code for the depictions of the stratospheric ozone concentration is described in
Figure 13.27 in the text; dark blue and violet colors represent a low concentration of stratospheric ozone,
while red and yellow are higher concentration.
Analyze
An elementary step represents a single collision process. Summing elementary steps will yield the overall
equation for the reaction that takes place. Intermediates are formed via an elementary step, then consumed by a
later step, while catalysts must be present for an initial step to occur, but are regenerated at the end of the
reaction. In both cases, the catalyst or intermediate is not present in the overall equation describing the reaction.
The greater the number of collisions between Cl atoms and O3 molecules in the atmosphere, the less ozone
should be present, and the larger the blue region should appear. We may rank [C], [F], and [I] by estimating the
size of the blue region and assigning these depictions to the greater number of collisions between Cl and O3.
Solve
(a) [A] and [H] are elementary steps in the chlorine-catalyzed decomposition of ozone. These steps are
Cl + O3 → ClO + O2
ClO + O3 → Cl + 2 O2
(b) The overall equation for the chlorine-catalyzed decomposition of ozone is
Cl + O3 → ClO + O2
+ ClO + O3 → Cl + 2 O2
2 O3 → 3 O 2
This overall process is depicted in [E].
62 | Chapter 13
(c) The elementary steps that combine to form a NO3 intermediate are [D] and [B]. These steps are
2 NO2 → NO + NO3
NO3 + CO → NO2 + CO2
(d) The overall equation with a NO3 intermediate is
2 NO2 → NO + NO3
+ NO3 + CO → NO2 + CO2
NO2 + CO → NO + CO2
(e) [G] depicts photochemical decomposition of a CFC. The equation is
CF2Cl2 → CF2Cl + Cl
(f ) [I]  [F]  [C]
Think About It
By examining the equations depicted here, we see how CFCs may cause damage to the ozone layer.
Chlorine atoms may be liberated from a CFC and catalyze the decomposition of O3 to O2. Since catalysts
are regenerated at the end of a reaction, a single Cl atom can lead to the decomposition of many O 3
molecules!

From Figure 13.4, we can see that the maximum concentration of NO 2 occurs later in the day than the
maximum concentration of NO. We are asked to explain why this is the case.
Analyze
One reaction involving NO and NO2 is described in Equation 13.2:
2 NO(g) + O2(g) → 2 NO2(g)
According to this equation, NO2 is generated from NO in the atmosphere.
Solve
As the concentration of NO increases in the atmosphere, more NO2 is generated. This process is not
immediate and will result in a decrease in the amount of free NO in the atmosphere as NO2 is generated.
The maximum concentration of NO2 will occur several hours after the maximum concentration of NO is
reached as a result of this delay, with a corresponding decrease in the concentration of NO as the above
reaction proceeds.
Think About It
NO is formed as a result of incomplete combustion of fuel in automobile engines. NO and the resulting
NO2 are major contributors to smog formation above urban centers.

By considering the levels of O3 during the day as seen in Figure 13.4, we are to explain why [O3]max occurs
later in the day than [NO]max and [NO2]max.
Analyze
Ozone in the troposphere (the lowest portion of Earth’s atmosphere) is due to the reaction of O 2 with O
generated from the interaction of UV light with NO2.
Solve
The presence of NO2 in the atmosphere and ample sunlight allows the O atoms to react with O 2 to generate
O3. The reactant NO2 is present in the atmosphere due to automobile exhaust building up during the day.
The buildup of O3 lags behind until later in the day, when [NO2] increases and the sunlight becomes
stronger as midday approaches.
Think About It
Ozone is a very reactive gas and is irritating to lung tissues.

We are asked to explain whether O atoms or O2 molecules are expected to be more reactive.
Analyze
O atoms have six valence electrons, two of which are unpaired (radicals). While O 2 also has unpaired
electrons, the covalent bonds present in this molecule mean that each O atom in O 2 has a complete octet.
Solve
O atoms are expected to be more reactive because of the unpaired electrons and incomplete octet.
Think About It
Oxygen radicals are powerful oxidants, leading to cell damage and the formation of other reactive species
such as ozone, O3.

We are asked why OH(g) is more reactive than H2O in the vapor phase.
Analyze
In the gas phase, OH is present as the hydroxyl radical, •OH. The hydroxyl radical has unpaired electrons
and an incomplete octet on oxygen. Water vapor is a molecular compound with a complete octet on oxygen
and no unpaired electrons.
Solve
The hydroxyl radical will react to restore the octet on oxygen, whereas water vapor is much more stable
and thus less reactive.
Think About It
Hydroxyl radicals have been found to react with many atmospheric gases, such as the greenhouse gases
methane and ozone.
64 | Chapter 13

We are asked to explain the difference between a rate of reaction and the rate constant for a reaction, at a
specific temperature.
Analyze
Recall that the rate of reaction is expressed in M/sec, while the units for the rate constant depend on the
order of the reaction.
Solve
The rate of a reaction is the overall change in the concentration of reactants and products, while the rate
constant for a reaction is the proportionality between the rate of the reaction and the concentration of each
reactant, raised to the order of each reactant.
Think About It
In some cases, the rate of reaction and rate constant may be identical. For example, a zero-order reaction
has a rate of reaction given by
rate = k[A]0 = k
In this case, the rate of reaction (rate) is equal to the rate constant (k) for the reaction.

We are to explain the difference between the average rate and the instantaneous rate of a reaction.
Analyze
The rate of reaction is measured by the change in concentration of a reactant or product over time. The
difference between the average and instantaneous rates is the length of the period of time over which the
change in concentration is measured.
Solve
The average rate is the rate averaged over a fairly long period of time, whereas the instantaneous rate is the
rate at a specific moment in time (or over a very, very short period of time).
Think About It
The rate of a reaction is always positive.

We are provided with an equation describing the decomposition of ethanal, forming methane and carbon
monoxide. By examining this reaction, we are asked how we could monitor its progress and whether these
methods would all give the same rate data.
Analyze
The rate of reaction is equal to the rate of appearance or disappearance of products or reactants, multiplied
by one over their stoichiometric coefficient from the balanced chemical reaction. For gases, we may use the
partial pressure of reactants or products to determine the rate of appearance or disappearance.
Solve
The reaction could be tracked by following the partial pressure of CH 3CHO (the pressure should decrease
over time), CH4 (the pressure should increase over time), or CO (the pressure should increase over time).
Additionally, we could track the total pressure. Since there are two moles of products and one mole of
reactants, as the reaction proceeds, the total pressure of the system will increase.
Think About It
Since all species in this equation have stoichiometric coefficients of one, the rates of appearance or
disappearance should all be numerically equal.

We are provided with an equation describing the decomposition of hydrogen peroxide, forming water and
oxygen gas. By examining this reaction, we are asked how we could monitor its progress and whether these
methods would all give the same rate data.
Analyze
The rate of reaction is measured by the change in concentration of a reactant or product over time. The
difference between the average and instantaneous rates is the length of the period of time over which the
change in concentration is measured. In this case, only oxygen would exert a significant partial pressure.
Practically speaking, it is difficult to measure the concentration of water, leaving hydrogen peroxide as the
other observable chemical entity.
Solve
We could follow the total pressure of the system, assuming that this corresponds to the partial pressure of
the O2 gas. We could also follow the concentration of H 2O2, which should decrease over time. Using these
values, the rate of appearance of O2 and disappearance of H2O2 should give the same overall rate of
reaction, assuming the correct units for the rate constant are used.
Think About It
Our assumption that Ptotal = PO2 is valid if we ignore the vapor pressure of water generated by this reaction.
At low total pressures, we may observe a more significant error.

We are asked to explain why the reaction between NaHCO3 and CaCl2 does not occur when solids are
mixed, but requires a solvent (water).
Analyze
The reaction being described here is a gas evolution reaction, in which two ionic species react to generate
CO2. The balanced equation is
CaCl2 (aq) + 2 NaHCO3 (aq) → CaCO3 ( s) + CO2 ( g ) + H 2O( ) + 2 NaCl(aq)
Solve
In solution, ionic compounds can dissociate and mix with one another. As solids, ions from the two
reactants are still bound to one another, so it is very unlikely that a reaction will occur on any significant
scale.
Think About It
Some reactions can proceed in the solid state, but these are much more rare than reactions that occur in
solution.
66 | Chapter 13

We are asked why reactions in the gas phase often have a faster rate of reaction at higher temperatures.
Analyze
When considering the behavior of gas-phase particles, we may employ kinetic molecular theory to explain
reactions. According to kinetic molecular theory, gas-phase particles travel in straight-line paths, forming
an activated complex (transition state) upon collision with another particle with sufficient energy and the
correct orientation.
Solve
As the temperature increases, the average kinetic energy of the particles increases. Particles move faster on
average, so there is an increased frequency of collisions. These collisions occur with greater energy, so a
higher percentage of collisions results in the formation of an activated complex, leading to a greater rate of
reaction.
Think About It
The changes to a system at higher temperature all affect the value of k, the rate constant. We can consider
individual contributions to the rate constant by examining the Arrhenius equation:
k = Ae- Ea / RT

We are asked to comment on the relationship between the rate of decomposition of A and the formation of
B in the reaction A → B + C.
Analyze
The rates of consumption of reactants and formation of products are related to the stoichiometric
coefficients of the reaction. From the balanced equation, the reaction may be expressed in terms of rates as
[A ] [B] [C]
Rate = - = + = +
t t t
Solve
The rate of formation of B and consumption of A are equal, but opposite in sign.
Think About It
Another way of stating this observation is that, for every mole of A consumed, one mole of B is formed,
and so the rates of consumption and formation are equal.

For the formation of ammonia from nitrogen and hydrogen, we are asked to comment on how the rates of
formation and decomposition are related to the mass of reactants and products.
Analyze
The rate of reaction may be expressed as
[N 2 ] 1 [H 2 ] 1 [NH 3 ]
Rate = - =- = +
t 3 t 2 t
As mentioned in the question, we see that the rate of formation of ammonia is twice the rate at which
nitrogen is consumed. However, the masses of the reactants and products are not equal to one another, so it
is not automatically true that the law of conservation of mass is being violated.
Solve
Mass remains constant in this reaction, and the law of conservation of mass applies. All atoms are
conserved throughout this transformation, but the number of molecules in which those atoms are distributed
changes. The rates of formation and consumption are tied to the molar concentration of reactants and
products, but the overall rate of reaction remains the same.
Think About It
Laws such as the law of conservation of mass are taken to be true statements about how chemical reactions
are conducted. If we were to observe evidence that is contrary to what is predicted by that law, either the
law must be discounted, or a flaw exists in our argument.

We are to determine if the rate of formation of a product will increase or decrease if the rate of consumption
of a reactant decreases (i.e., becomes less negative).
Analyze
Graphically, this question is asking how the rate of reaction with respect to the concentration of product
changes as the reaction proceeds [i.e., from (a) to (c)]:
Solve
If a reactant is consumed less rapidly (e.g., at point (c) compared to point (a)), then product will also be
produced less rapidly.
Think About It
As more product is formed, the rate of change in the concentration of product will decrease. In general, the
instantaneous rate of reaction at the outset of the reaction is fast, after which the reaction begins to slow
down.

We are asked what conditions might lead to a reaction having no change in the rate of reaction.
Analyze
The rate of reaction is the rate of net change between the concentration of products and reactants.
Solve
At dynamic equilibrium, there is no net change in the concentrations of reactants and products, so there
would be no change in the rate of reaction.
68 | Chapter 13
Think About It
If a reaction has reached equilibrium, it is common to push the reaction to completion by adding additional
reactants or removing products.

We may determine the relationship between the rate of formation of N 2, the rate of formation of O2, and the
rate of consumption of NO in an automotive catalytic converter by examining the reaction.
Analyze
The reaction that occurs in the catalytic converter is
2 NO(g) → N2(g) + O2(g)
From the balanced equation, the reaction may be expressed in terms of rates as
1 [NO ] [N 2 ] [O 2 ]

Rate = - = + = +
2 t t t
Solve
(a) The relationship between [O2] and [N2] is
[N 2 ] [O 2 ]
=
t t
(b) The relationship between [NO] and [N2] is
[N 2 ] 1 [NO ]
=-
t 2 t
Think About It
The rate of change in concentrations of reactants and products is related to the stoichiometry of the reaction
being considered.

We may determine the relationship between the rate of formation of CO2, the rate of consumption of O2,
and the rate of consumption of CO in an automotive catalytic converter by examining the reaction.
Analyze
The reaction that occurs in the catalytic converter is
2 CO(g) + O2(g) → 2 CO2(g)
1  [CO ]  [O 2 ] 1  [CO 2 ]
Rate = - =- = +
2 t t 2 t
Solve
(a) The relationship between [O2] and [CO2] is
 [CO 2 ]  [O 2 ]
= - 2´
t t
(b) The relationship between [CO] and [CO2] is

[CO 2 ] [CO ]
=-
t t
Think About It
Most automotive catalytic converters convert CO, NO, and uncombusted fuel into more harmless species.

Using the balanced equations provided, we are to write expressions to compare the rates of formation of
products and the rates of consumption of reactants.
Analyze
For the reaction a A + b B → c C + d D, the rate of reaction may be expressed as
1 [A ] 1 [B] 1 [C ] 1 [D ]

Rate = - =- = + = +
a t b t c t d t
Solve
[F2 ] [HOF] [HF]
(a) Rate = - = + = +
t t t

1 [ HCl ]  [ 2]
H
(b) Rate = - = +
3 t t
1 [NH 3 ] 1 [O 2 ] 1 [N 2 ] 1 [H 2O ]
(c) Rate = - =- = + = +
4 t 4 t 2 t 6 t
Think About It
As for equilibrium expressions, pure liquids and solids are excluded from the rate law.

Using the balanced equations provided, we are to write expressions to compare the rates of formation of
products and the rates of consumption of reactants.
Analyze
For the reaction a A + b B → c C + d D, the rate of reaction may be expressed as
1  [A ] 1  [B] 1  [C ] 1  [D ]
Rate = - =- = + = +
a t b t c t d t
NH4Cl(s) will not appear in the rate expression for (c) since it is a solid, and thus, its concentration will
not change.
Solve
 [SOF2 ] 1  [F2 ]  [F5SOF]
(a) Rate = - =- = +
t 2 t t
 [B2H 6 ] 1  [Cl2 ] 1  [BCl3 ] 1  [HCl ]
(b) Rate = - =- = + = +
t 6 t 2 t 6 t
 [N 2H 4 ] 1  [NH 2Cl]  [N 2 ]
(c) Rate = - =- = +
t 2 t t
70 | Chapter 13
Think About It
Since all species in these rate expressions are in the gas phase, we could also use partial pressures instead
of concentrations.

Given the concentration of NO(g) at two times along a reaction profile, we may determine the rate of the
reaction.
Analyze
The reaction under consideration is
NO(g) + O2(g) → 2 NO2(g)
 [NO ]  [O 2 ] 1  [NO 2 ]
Rate = - =- = +
t t 2 t
where [NO] is the difference of the two provided concentrations, and t is the difference of the
corresponding times. We may substitute the provided values for [NO] and time into this expression and
solve for the rate.
Solve
æ0.0225 M - 0.0300 M ÷
ö
Rate = - çç ÷
÷ = 5.81´ 10- 6 M /s
çè 650.0 s - 5.0 s ø
Think About It
The rate of reaction will always be positive. In this case, the −1 coefficient and decreasing concentration of
NO lead to a positive rate, but the same value could be obtained from data for the appearance of NO2 or
disappearance of O2.

Given the rate of reaction for the production of ammonia, we may calculate the average rate of
disappearance of H2(g).
Analyze
The reaction under consideration is
2 NH3(g) → N2(g) + 3 H2(g)
1  [NH 3 ]  [N 2 ] 1  [H 2 ]
Rate = - = + = +
2 t t 3 t
We may rearrange this equation and solve for the rate of reaction or rate of change by substituting in the
rate of decomposition of ammonia. Rearranging the equation to solve for the requested quantities gives
 [H 2 ] 3  [NH 3 ]
=-
t 2 t
 [N 2 ] 1  [NH 3 ]
=-
t 2 t
1  [NH 3 ]
Rate = -
2 t
Solve
 [H 2 ] 3
(a) = - (- 0.38 M /s) = 0.57 M /s
t 2
 [N 2 ] 1
(b) = - (- 0.38 M /s) = 0.19 M /s
t 2
1
(c) Rate = - (- 0.38 M /s) = 0.19 M /s
2
Think About It
The rate of consumption of NH3 and the rate of formation of H2 are related by the stoichiometry of this
reaction, but neither value is equal to the average rate of reaction. For this example, the rate of reaction
is +0.19 M/s.

Using the balanced equation describing the reaction of SO 2 with CO, we are to write expressions to
compare the rates of formation of products and the rates of consumption of reactants.
Analyze
From the balanced equation we see that the reaction may be expressed as
 [SO 2 ] 1  [CO ] 1  [CO 2 ]  [COS]
Rate = - =- = + = +
t 3 t 2 t t
Solve
 [CO 2 ] 2  [CO ]
(a) Rate = =-
t 3 t
 [COS]  [SO 2 ]
(b) Rate = =-
t t
 [CO ]  [SO 2 ]
(c) Rate = = 3
t t
Think About It
These relative rates make sense based on the stoichiometry of the reaction. For every 1 mole of SO2 used in
the reaction, 2 moles of CO2 and 1 mole of COS are produced. So, for example, the concentration of CO 2
will increase twice as fast as the concentration of SO2 decreases.

Using the balanced equation describing the reaction of CH4 with NO, we are to write expressions to
compare the rates of formation of products and the rates of consumption of reactants.
Analyze
From the balanced equation we see that the reaction may be expressed as
 [CH 4 ] 1  [NO ] 1  [N 2 ]  [CO 2 ] 1  [H 2O ]
Rate = - =- = + = + = +
t 4 t 2 t t 2 t
72 | Chapter 13
Solve
 [N 2 ]  [CO 2 ]
(a) Rate = = 2
t t
 [CO 2 ] 1  [NO ]
(b) Rate = =-
t 4 t
 [CH 4 ] 1  [H 2O ]
(c) Rate = - =
t 2 t
Think About It
The negative sign is used in front of the expressions involving the consumption of a reactant to give a
positive reaction rate because the change in concentration, [X] f − [X]i or [X], is negative for reactants
because [X]f  [X]i.

Using the relative rate expressions and the rate of the consumption of ClO in two reactions, we are to
calculate the rate of change in the formation of the products of the two reactions.
Analyze
(a) For this reaction:
1  [ClO ]  [Cl2 ]  [O 2 ]
Rate = - = + = +
2 t t t
(b) For this reaction:
 [ClO ]  [O3 ]  [O 2 ]  [ClO 2 ]
Rate = - =- = + = +
t t t t
For each reaction we are given [ClO]/t, and we can use this value in the relationships above to calculate
the rate of change in (a) the concentration of Cl2 and O2 and (b) the concentration of O2 and ClO2.
Solve
 [Cl2 ]  [O 2 ] 1  [ClO ] 1
(a) = = - = - ´ - 2.3´ 107 M /s
t t 2 t 2
= 1.2 ´ 107 M /s
 [O 2 ]  [ClO 2 ]  [ClO ]
(b) = = - = - (- 2.9 ´ 104 M /s )
t t t
= 2.9 ´ 104 M /s
Think About It
The rates of the formation of products is positive because [X]f  [X]i, so [X]f − [X]i = [X] is positive.

Using the relative rate expressions and the given rates of the consumption of NO 3 in two reactions, we can
calculate the rates of change in the formation of the products of the two reactions.
Analyze
 [NO3 ]  [NO ] 1  [NO 2 ]
(a) - =- = +
t t 2 t
1  [NO3 ] 1  [NO 2 ]  [O 2 ]
(b) - = + = +
2 t 2 t t
For each reaction we are given [NO3]/t, and we can use this value in the rate relationships to calculate
the rates of change in the concentration of NO2.
Solve
1  [NO2 ]  [NO3 ]  [NO2 ]  [NO3 ]
(a) =- or =- 2
2 t t t t
= - 2´ (- 2.2´ 105 mM /min )
= 4.4´ 105 mM /min
1  [NO 2 ] 1  [NO3 ]  [NO 2 ]  [NO3 ]

(b) =- or =-
2 t 2 t t t
= - (- 2.3 mM /min )
= 2.3 mM /min
Think About It
Because we always express the rate of reaction as a positive value, we assign to the rate of consumption of
a reactant a negative sign because [X]f − [X]i  0 since [X]f  [X]i.

Given the [O3] over time when it reacts with NO2−, we are to calculate the average reaction rate for two
time intervals.
Analyze
The average rate of reaction can be found according to
 [O3 ] [O3 ]f - [O3 ]i

=
t tf - ti
Solve
Between 0 and 100 s:
 [O3 ] (9.93´ 10 - 1.13´ 10 )M

- 3 - 2
- = = 1.4´ 10- 5 M /ms

t (100 - 0)ms
Between 200 and 300 s:
 [O3 ] (8.15´ 10 - 8.70´ 10 )M

- 3 - 3
- = = 5.50´ 10- 6 M /ms

t (300 - 200 )ms
Think About It
Notice that as the reaction proceeds, the rate of consumption of ozone decreases. This is due to the
decreasing reactant concentrations.
74 | Chapter 13

Given the [N2O5] over time as it decomposes, we are to calculate the average rate of the reaction between
all the consecutive times for the data presented.
Analyze
The average rate of the reaction can be found according to
 [N 2O5 ] [N 2O5 ]f - [N 2O5 ]i

=
t tf - ti
Solve
Between 0 and 1.45 s:
 [N 2O5 ] (1.357 ´ 10 - 1.500´ 10 )molecules/cm

12 12 3
- = = 9.86´ 1010 molecules/(cm3 ×s)

t (1.45 - 0)s
Between 1.45 s and 2.90 s:
 [N 2O5 ] (1.228´ 10 - 1.357 ´ 10 )molecules/cm

12 12 3
- = = 8.90´ 1010 molecules/(cm3 ×s)

t (2.90 - 1.45)s
 [N 2O5 ] (1.111´ 10 - 1.228´ 10 )molecules/cm

12 12 3
- = = 8.07 ´ 1010 molecules/(cm3 ×s)

t (4.35 - 2.90)s
 [N 2O5 ] (1.005´ 10 - 1.111´ 10 )molecules/cm

12 12 3
- = = 7.31´ 1010 molecules/(cm3 . s)

t (5.80 - 4.35 )s
Think About It
Notice that as the reaction proceeds the rate of disappearance of dinitrogen pentoxide decreases. This is
due, in part, to the decreasing reactant concentrations.

After we plot [ClO] versus time and [Cl2O2] versus time, we can determine the instantaneous rate of change
at 1 s for each compound.
Analyze
The instantaneous rate is the slope of the line that is tangent to the curve at the time we are interested in.
We can estimate fairly well the instantaneous rate at 1 s from the plots by choosing two points that are
close to 1 s to calculate the slope. Since we are given only values for [ClO], we need to calculate [Cl 2O2]
for each time:
([ClO]0 - [ClO]t )
[Cl2O2 ]t =
2
where [ClO]0 = 2.60  10 M.11
Time [ClO]t [Cl2O2]t

s molecules/cm3 molecules/cm3
0 2.60  1011 0.00
1 1.08  1011 7.60  1010
2 6.83  1010 9.59  1010
3 4.99  1010 1.05  1011
4 3.93  1010 1.10  1011
5 3.24  1010 1.14  1011
6 2.76  1010 1.16  1011
Note that initially there is no Cl2O2 present, so [Cl2O2]0 = 0 molecules/cm3.
Solve
For the change in concentration of ClO versus time we obtain the following plot:
To get a fairly good estimate from the data given for the instantaneous rate, we can choose two points from
the data set that surrounds the data point of interest and calculate [ClO]/t.
For t = 1 s, we can use the points t = 0 s and t = 2 s:
 [ClO] (6.83´ 10 - 2.60´ 10 )molecules/cm

10 11 3
- = = 9.6´ 1010 molecules/(cm3 ×s)

t (2 - 0)s
Using a graphing program that calculates the slope of the tangent to the line at t = 1 s, we get an
instantaneous rate of 8.3  1010 molecules  cm−3  s.
For the change in concentration of Cl2O2 versus time we obtain the following plot:
76 | Chapter 13
the data set that surrounds the data point of interest and calculate [Cl2O2]/t.
For t = 1 s, we can use the points t = 0 s and t = 2 s:
 [Cl2O2 ] (9.59´ 10 - 0)molecules/cm

10 3
= = 4.8´ 1010 molecules/(cm3 ×s)

t (2 - 0)s
Using a graphing program that calculates the slope of the tangent to the line at t = 1 s, we get an
instantaneous rate of 4.1  1010 molecules  cm−3  s.
Think About It
Because we expect the rate of disappearance of ClO to be twice the rate of appearance of Cl 2O2 from the
balanced equation
2 ClO(g) → Cl2O2(g)
our answers make sense:
æ [ClO]ö÷
çç ÷
ççè t ø÷
÷ 9.6´ 1010 molecules/(cm3 ×s)
= = 2.0
æ [Cl2O 2 ]ö÷ 4.8´ 1010 molecules/(cm3 ×s)
çç ÷
ççè t ø÷ ÷

To determine the instantaneous rate of the reaction of O3 with NO at 0.000 s and 0.052 s, we have to plot
[NO] versus time.
Analyze
On the plot, we will draw the tangents to the line where t = 0.00 s and t = 0.052 s. The slopes of these lines
are the instantaneous rates of the reaction. We can estimate fairly well from the plot the instantaneous rate
at the two times during the reaction by choosing two points from the data set that surrounds the times of
interest to calculate the slope.
Solve
the data set that surrounds the data point of interest and calculate [NO]/t.
For t = 0.00, we can use the points t = 0.00 and t = 0.011:
-
 [NO ]
=-
(1.8´ 10- 8 - 2.0´ 10- 8 )M = 1.8´ 10- 7 M /s
t (0.011- 0)s
Using a graphing program that calculates the slope of the tangent to the line at t = 0.00 s, we get an
instantaneous rate of 1.9  10−7 M/s.
For t = 0.052 we can use the points t = 0.027 s and t = 0.102 s:
-
 [NO ]
=-
(1.2´ 10- 8 - 1.6´ 10- 8 )M = 5.3´ 10- 8 M /s
t (0.102 - 0.027)s
Using a graphing program that calculates the slope of the tangent to the line at t = 0.052 s, we get an
instantaneous rate of 6.3  10−8 M/s.
Think About It
Notice that as the reaction progresses the rate of the reaction decreases.

We are asked to explain why the rate of a reaction generally decreases as the reaction proceeds.
Analyze
As a reaction proceeds, products are formed and the concentration of products increases, while reactants are
consumed and the concentration of reactants decreases. The rate of a reaction depends on the concentration
of reactants.
Solve
As the concentration of reactants decreases, so too will the number of collisions between reactants. It is
thus less likely that reactants will collide with sufficient energy and the proper orientation to overcome the
activation energy for the reaction, and the rate decreases.
Think About It
By the same rationale, kinetic molecular theory suggests that as the temperature increases, so does the
average energy of the reactants, and so it is more likely that reactants will have sufficient energy to
overcome the activation energy when colliding. For this reason, most reactions have a higher rate of
reaction at higher temperatures.

We are to explain why the units of the rate constant change with the overall order of the reaction.
Analyze
The form of the rate law is
Rate = k[A]x
Rearranging and solving for k:
rate
k= x
[A ]
78 | Chapter 13
Solve
The rate of a reaction is expressed as concentration per time (often in M/s), and the concentration of A is
usually expressed in moles per liter (M ). The order of the reaction may be any number (fractional, whole
numbers, or even negative). It is the order of the reaction that changes the units of k. Some examples are as
follows:
M /s
For a first-order reaction, k = = s- 1
M
M /s
For a third-order reaction, k = = M - 2 ×s- 1
M3
M /s
For a one-half-order reaction, k = = M 1/ 2 ×s- 1
M 1/ 2
Think About It
Once the form of the rate law is known, we can determine the units of the rate constant.

Given some information about the rate constant and temperature, we are asked to determine the order of a
reaction.
Analyze
The units of the rate constant differ depending on the order of the reaction. The units for the rate constant of
a zero-order reaction are M  s−1, for a second-order reaction are s−1, and for a third-order reaction are
M−1  s−1.
Solve
Matching the units on the rate constant provided to those listed above, we see that 2.5  102 M/s corresponds
to a zero-order reaction.
Think About It
For a zero-order reaction, the rate of reaction does not depend on the concentration of the reactant.

We are asked whether the rate of reaction increases for a zero-, first-, or second-order reaction.
Analyze
A plot of rate of reaction versus times for zero-, first-, and second-order reactions is below:
As a reaction proceeds, products are formed and the concentration of products increases, while reactants are
consumed and the concentration of reactants decreases. The rate of a reaction depends on the concentration
of reactants.
Solve
None of these reaction orders will exhibit an increase in the rate of reaction as the reaction proceeds. In the
case of a zero-order reaction, the rate will remain the same, while for a first- and second-order reaction, the
rate will decrease.
Think About It
Alternately, you might imagine the effect of a decreasing concentration on the rate law for the reaction. For
the reaction
A → products
the form of the rate law is
Rate = k[A]x
As the reaction proceeds and [A] decreases, the rate of reaction will decrease or stay the same, but not
increase.

For a second-order reaction, we are to predict the effect of doubling [A] 0 on the half-life.
Analyze
For a second-order reaction:
1
t1/ 2 =
k [A ]0
Solve
From the equation for the half-life of a second-order reaction, we see that doubling [A]0 halves the half-life.
Think About It
The half-life of a second-order reaction, like that of a first-order reaction, is inversely related to the rate
constant.

We are asked to consider the conditions under which two second-order reactions with the same rate
constant would have the same half-life.
Analyze
The half-life for a second-order reaction is given by
1
t1/ 2 =
k [A ]0
Since k is the same for both reactions, the initial concentrations of A or X are the only parameters that we
need to consider.
80 | Chapter 13
Solve
If [A]0 = [X]0, the two half-life expressions will be equal:
1 1
t1/ 2 = =
k [A ]0 k [X ]0
Think About It
It is unusual for two reactions to have exactly the same rate constant at a given temperature, unless the
value is determined with few significant figures.

For each rate-law expression, we are to determine the order of the reaction with respect to each reactant and
the overall reaction order.
Analyze
The order of a reaction is the experimentally determined dependence of the rate of a reaction on the
concentration of the reactants involved in the reaction. In the rate-law expression, the order is shown as the
power to which the concentration of a particular reactant is raised. The overall reaction order is the sum of
the powers of the reactants in the rate-law expression.
Solve
(a) For Rate = k[A][B], the reaction is first order in both A and B and second order overall.
(b) For Rate = k[A]2[B], the reaction is second order in A, first order in B, and third order overall.
(c) For Rate = k[A][B]3, the reaction is first order in A, third order in B, and fourth order overall.
Think About It
The higher the order of the reaction for a particular reactant, the greater the effect of a change in
concentration of that reactant on the reaction rate.

For each rate-law expression, we are to determine the order of the reaction with respect to each reactant and
the overall reaction order.
Analyze
The order of a reaction is the experimentally determined dependence of the rate of a reaction on the
concentration of the reactants involved in the reaction. In the rate-law expression, the order is shown as the
power to which the concentration of a particular reactant is raised. The overall reaction order is the sum of
the powers of the reactants in the rate-law expression.
Solve
(a) For Rate = k[A]2[B]1/2, the reaction is second order in A, one-half order in B, and two and one-half
order overall.
(b) For Rate = k[A]2[B][C], the reaction is second order in A, first order in both B and C, and fourth order
overall.
(c) For Rate = k[A][B]3[C]1/2, the reaction is first order in A, third order in B, one-half order in C, and four
and one-half order overall.
Think About It
The higher the order of the reaction for a particular reactant, the greater the effect of a change in
concentration of that reactant on the reaction rate.

For each of the reactions described, we are to write the rate law and determine the units for k, using the
units M for concentration and s for time.
Analyze
The general form of the rate law is
Rate = k[A]x[B]y
where k is the rate constant, A and B are the reactants, and x and y are the orders of the reaction with
respect to each reactant as determined by experiment.
Solve
(a) Rate = k[O][NO2]
Because rate has units of M/s and each concentration has units of M,
M /s
k= = M - 1 ×s- 1
M2
(b) Rate = k[NO]2[Cl2]
M /s
k= = M - 2 ×s- 1
M3
(c) Rate = k [CHCl3 ][Cl 2 ]1/ 2
M /s
k= = M - 1/ 2 ×s- 1
M 3/ 2
(d) Rate = k[O3]2[O]−1
M /s
k= = s- 1
M 2/M
Think About It
The units of the rate constant clearly depend on the overall order of the reaction.

Given the order of the reaction for each of the reactants in the chemical reaction
A+B→C
we are to write the rate-law expression and determine the units of the rate constant k, using the units M for
concentration and s for time.
Analyze
In the rate-law expression, the order of the reaction for each reactant is placed as an exponent to the
concentration:
Rate = k[A]x[B]y
where x and y are the orders of the reaction with respect to A and B. The rate of the reaction is expressed as
M/s, so the rate constant units will have to be 1/Mz−1  s where z is the overall order of the reaction.
82 | Chapter 13
Solve
(a) Rate = k[A][B]2 with k in units of 1/M 2  s
(b) Rate = k[A][B] with k in units of 1/M  s
(c) Rate = k[B]2 with k in units of 1/M  s
(d) Rate = k[A]2[B]2 with k in units of 1/M 3  s
Think About It
A reaction rate that is independent of the concentration of a reactant is zero order with respect to that
reactant. So for part (c),
Rate = k[A]0 [B]2
where [A]0 = 1.

Given the changes in rate of the decomposition of BrO to Br 2 and O2 when [BrO] is changed, we are to
predict the rate-law expression in each case.
Analyze
The general form of the rate law for the reaction is
Rate = k[BrO]x
where x is an experimentally determined exponent.
Solve
(a) If the rate doubles when [BrO] doubles, then x = 1 and the rate law is
Rate = k[BrO]
(b) If the rate quadruples when [BrO] doubles, then x = 2 and the rate law is
Rate = k[BrO]2
(c) If the rate is halved when [BrO] is halved, then x = 1 and the rate law is
Rate = k[BrO]
(c) If the rate is unchanged when [BrO] is doubled, then x = 0 and the rate law is
Rate = k[BrO]0 = k
Think About It
For this reaction, the relationship between the change in rate when the concentration of the reactant was
changed to determine x is straightforward. To determine x for more complicated reactions, use
rate 2 æ öx
çç[A ]2 ÷
÷
= ÷
rate1 ççè [A ]1 ÷
÷
ø
ærate 2 ÷ ö æ[A ] ÷ ö
ln çç çç 2 ÷
÷ = x ln çç A ÷ ÷
çè rate1 ÷
ø è [ ]1 ÷
ø
ærate 2 ö ÷
ln çç ÷
çè rate1 ÷ ø
x=
æ[A ] ÷ ö
ln ççç 2 ÷ ÷
çè [A ]1 ÷
÷
ø

Using the information of how the rate of the reaction changes when the concentration of a reactant is
changed, we can predict the rate law for the reaction of NO with Br 2 to give NOBr2.
Analyze
(a) If the rate doubles when [NO] doubles while [Br2] remains constant, then the reaction is first order in NO.
(b) If the rate doubles when [Br2] doubles while [NO] remains constant, then the reaction is first order in Br2.
(c) If the rate of the reaction increases by 1.56 times when [NO] increases by 1.25 times while [Br 2]
remains constant, then the order of the reaction for NO is
1.25x = 1.56
x ln(1.25) = ln(1.56)
x = 1.993 = 2
(d) If the rate is halved when [NO] is doubled and [Br 2] remains constant, then the order of the reaction of
NO is
2x = 0.5
x ln(2) = ln(0.5)
x = −1
Solve
(a) Rate = k[NO][Br2]y where y is undefined
(b) Rate = k[NO]y[Br2] where y is undefined
(c) Rate = k[NO]2[Br2]y where y is undefined
(d) Rate = k[Br2]y[NO]−1 where y is undefined
Think About It
The order for a particular reactant in a rate-law expression may be any number (positive, negative, zero,
fraction, or whole) and can only be determined by experiment, not by looking at the overall balanced
chemical equation.

We must predict possible reaction orders when doubling both reactant concentrations leads to a rate that is
four times the initial rate.
Analyze
The reaction being considered is
NO(g) + O3(g) → NO2(g) + O2(g)
We may consider possible rate laws to account for this observation, arising from common reaction orders
with respect to the reactants, NO and O3.
Solve
At least two possible rate laws satisfy the quadrupling of rate. If the reaction is first order in each reactant,
the rate is expected to quadruple.
1 1 1 1
rateb [NO]b [O3 ]b (2) (2)
= = = 4
ratea [NO]1 [O3 ]1 1
(1) (1)
1
a b
If the reaction is second order in one reactant and zeroth order in the other, the rate is also expected to
quadruple.
84 | Chapter 13
2 0 2 0
rateb [NO]b [O3 ]b (2) (2)
= = = 4
ratea [NO]2 [O3 ]0 2
(1) (1)
0
a b
Since both situations could lead to the same observed rate behavior, it is not conclusive that the reaction is
first order in both reactants.
Think About It
In order to determine the rate law for this reaction, the concentrations of NO and O3 must be manipulated
independently. For example, doubling [NO] while holding [O 3] constant would have different effects on
the rate:
1 1 1 1
rate b [NO ]b [O3 ]b (2) (1)
= = = 2
ratea [NO ]1 [O3 ]1 1
(1) (1)
1
a b
2 0 2 0
rate b [NO ]b [O3 ]b (2) (1)
= = = 4
ratea [NO ]2 [O3 ]0 (1)
2
(1)
0
a b

Given that the reaction between M (a molecule that is unchanged in the reaction) with ClO and NO2 is first
order in NO2 and in ClO, we are to write the rate law and determine the order of the reaction for M.
Analyze
Knowing that the reaction is first order in both NO 2 and ClO means that the exponent for the concentrations
in the rate law for both of these reactants is 1. Because no dependence on the rate was given in the problem
for M, we can assume that changing [M] does not affect the rate of the reaction.
Solve
(a) Rate = k[ClO][NO]
(b) For the rate law to show no dependence on [M], the order of the reaction with respect to M must
be zero.
Think About It
The molecule M may function in this reaction to transfer energy from one of the reactants to another to
enable the reaction to take place or to bring the reactants closer together to facilitate the reaction between
them.

For the reaction of NO2 with O3 to produce NO3 and O2, we are to write the rate law given that the reaction
is second order overall. From the rate law and given the rate constant, we can calculate the rate of the
reaction for a given [NO2] and [O3]. From this we can calculate the rate of appearance of NO 3 and the rate
of the reaction when [O3] is doubled.
Analyze
The general form of the rate law for this reaction is
Rate = k[NO2]x[O3]y
The rate of consumption of reactants and formation of products is
 [NO 2 ]  [O3 ]  [NO3 ]  [O 2 ]
Rate = - =- = + = +
t t t t
Solve
(a) Rate = k[NO2][O3]
1.93´ 104
(b) Rate = ´ 1.8´ 10- 8 M ´ 1.4´ 10- 7 M = 4.9´ 10- 11 M /s
M ×s
 [NO3 ]
(c) Rate = = 4.9´ 10- 11 M /s
t
(d) When [O3] is doubled, the rate of the reaction doubles.
Think About It
When [O3] = 2.8  10−7 M (double that in part (b)), the rate of reaction is 9.73  10−11 M/s, which is twice
that calculated in part (b), so our prediction in part (d) is correct.

We are to write the rate law for the reaction between N 2O5 and H2O, and from that rate law we are to
calculate the rate constant for the reaction given a reaction rate and concentrations of N 2O5 and H2O.
Analyze
We are given that the reaction is first order in both reactants, so the exponents for the concentrations of
both N2O5 and H2O are 1. To calculate k we rearrange the rate law to solve for k and use the given rate of
the reaction and the concentrations of the reactants in the equation.
Solve
(a) Rate = k[N2O5][H2O]
rate 4.55´ 10- 4 mM / min
(b) k = = = 1.50´ 10- 5 mM - 1 ×min- 1
[N2O5 ][H2O] 0.132 mM ´ 230 mM
Think About It
The rate constant does not change (except with temperature), although changing the initial concentrations
of the reactants would change the rate of the reaction.

By comparing the rate constants for four reactions that are all second order, we can determine which
reaction is the fastest if all the initial concentrations are the same.
Analyze
The reaction with the largest rate constant has the fastest reaction rate.
Solve
Reaction (c) has the largest value of k, so it proceeds the fastest.
Think About It
The slowest reaction is a reaction with the smallest value of k.

Given a first-order reaction and a second-order reaction, each with the same rate constant, we are to
indicate which reaction will proceed faster when the reactants are both 1.0 mM or 2.0 M.
86 | Chapter 13
Analyze
The first-order reaction rate law is
RateA = k[A]
The second-order reaction rate law is
RateB = k[B]2
Solve
(a) Neither. If the initial concentrations of A and B are both 1.0 mM, the reaction rates are identical
because
RateA = k[1.0 mM]
RateB = k[1.0 mM]2
RateA = RateB
(b) If the initial concentrations of A and B are both 2.0 M, the reaction rates differ:
RateA = k[2.0 M]
RateB = k[2.0 M]2 = k  4.0 M 2
For these concentrations of reactants, the second-order reaction proceeds faster.
Think About It
For these two reactions, any [A] = [B] less than 1.0 mM will have a faster rate for the first-order reaction,
but for [A] = [B] greater than 1.0 mM the second-order reaction will be faster.

Given a rate constant of 3.4  10−5 s−1, we are asked to write a rate law describing the reaction
2 N2O5(g) 4 NO2(g) + O2(g)
Analyze
The rate law for a reaction is equal to the rate constant multiplied by the concentration of each reactant
raised to its order. Since the only reactant is N 2O5, it will be the only concentration appearing in the rate
law. The units of the rate constant (s−1) tell us that this reaction is first order.
Solve
The rate law for this reaction is
Rate = 3.4  10−5 s−1[N2O5]1
Think About It
The rate, expressed in terms of individual reactant and product concentrations, is
1  [N 2O5 ] 1  [NO 2 ]  [O 2 ]
Rate = - = + = +
2 t 4 t t

Given the effect on the rate of the reaction between HO2 and SO3 when their concentrations are doubled,
we can write the rate law for the reaction.
Analyze
If the rate of the reaction doubles when either reactant concentration is doubled, then the exponent for each
reactant in the rate law expression is 1.
Solve
Rate = k[HO2][SO3]
Think About It
Although this reaction is first order in each reactant, it is second order overall.

In the reaction of ClO2 with OH−, the rate of the reaction was measured for various concentrations of both
reactants. From the data, we are to determine the rate law and calculate the rate constant, k.
Analyze
To determine the dependence of the rate on a change in the concentration of a particular reactant, we can
compare the reaction rates for two experiments in which the concentration of that reactant changes but the
concentrations of the other reactants remain constant. Once we have the order of the reaction for each
reactant, we can write the rate-law expression. To calculate the rate constant for the reaction, we can
rearrange the rate law to solve for k and use the data from any of the experiments.
Solve
Using experiments 1 and 2, we find that the order of the reaction with respect to ClO 2 is 1:
æ öx
rate1 çç [ClO 2 ]0,1 ÷ ÷
=ç ÷
rate 2 ççè[ClO 2 ]0,2 ø÷
÷
0.0248 M /s æ0.060 M ÷öx

= çç ÷
0.00827 M /s çè 0.020 M ø÷
3.00 = 3.01x
x= 1
Using experiments 2 and 3, we find that the order of the reaction with respect to [OH−] is also 1:
x
æé - ù ö÷
rate3 çç êëOH úû0,3 ÷
÷
= çç
rate 2 ççêéOH- ù ÷ ÷
èë úû0,2 ÷÷
ø
0.0247 M /s æ0.090 M ö÷x

= çç ÷
0.00827 M /s çè 0.030 M ÷ø
2.99 = 3.0 x
x= 1
The rate law for this reaction is Rate = k[ClO2][OH−].
Rearranging the rate-law expression to solve for k and using the data from experiment 1 give
88 | Chapter 13
rate 0.0248 M /s
k= = = 14 M - 1 s- 1
[ClO 2 ][OH- ] 0.060 M ´ 0.030 M
Think About It
We may use any of the experiments in the table to calculate k. Each experiment’s data give the same value
of k as long as the experiments were all run at the same temperature.

From the data collected for the production of nitrate from the reaction of NO 2− with O3, we are to determine
the rate law and calculate the rate constant, k.
Analyze
reactant, we can write the rate-law expression. To calculate the rate constant for the reaction, we can
rearrange the rate law to solve for k and use the data from any of the experiments.
Solve
Using experiments 1 and 2, we find that the order of the reaction with respect to NO 2− is 1:
x
æé - ù ö
rate 2 çç ëêNO 2 ûú0,2 ÷ ÷
÷
=ç ÷
rate1 ççç éêNO 2- ùú ÷ ÷
èë û0,1 ø÷
x
37.5 M /s æ 0.0150 M ö÷
= çç ÷
25 M /s çè 0.0100 M ÷ø
1.5 = 1.50 x
x= 1
Using experiments 3 and 4, we find that the order of the reaction with respect to O 3 is also 1:
æ öx
rate4 çç[O3 ]0,4 ÷÷
=ç ÷
rate3 ççè[O3 ]0,3 ÷
÷
ø
x
200.0 M /s æ 0.0200 M ö÷
= çç
50.0 M /s çè 0.0050 M ø÷
÷
4.00 = 4.0 x
x= 1
The rate law for this reaction is Rate = k[NO2 ][O3].
−
rate 25 M /s
k= = = 5.0´ 105 M - 1 ×s- 1
[NO 2- ][O3 ] 0.0100 M ´ 0.0050 M
Think About It

In the reaction of H2 with NO, the rate of the reaction was measured for various concentrations of both
reactants. From the data we are to determine the rate law and calculate the rate constant, k.
Analyze
concentrations of the other reactants remain constant. Once we have the order of the reaction with respect
to each reactant, we can write the rate-law expression. To calculate the rate constant for the reaction, we
can rearrange the rate law to solve for k and use the data from any of the experiments.
Solve
Using experiments 1 and 2, we find that the order of the reaction with respect to NO is 2:
æ öx
rate2 çç[NO]0,2 ÷ ÷
=ç ÷
rate1 ççè [NO ]0,1 ø÷
÷
x
0.0991 M /s æ 0.272 M ö÷
= çç ÷
0.0248 M /s çè 0.136 M ø÷
4.00 = 2.00 x
x= 2
Using experiments 3 and 4, we find that the order of the reaction with respect to H 2 is 1:
æ öx
rate 4 çç[H 2 ]0,4 ÷÷
=ç ÷
÷
rate3 ççè[H 2 ]0,3 ø÷
1.59 M /s æ0.848 M ö÷x

= çç ÷
0.793 M /s çè 0.424 M ÷ø
2.01 = 2.00 x
x= 1
The rate law for this reaction is Rate = k[NO]2[H2].
0.0248 M /s
k= 2
= 6.32 M - 2 ×s- 1
(0.136 M ) ´ 0.212 M
Think About It

In the reaction of NO2 with CO, the rate of the reaction was measured for various concentrations of both
reactants. From the data we are to determine the rate law and calculate the rate constant, k. We are also to
calculate the rate of formation of CO2 when [NO2] = [CO] = 0.500 M.
90 | Chapter 13
Analyze
concentrations of the other reactants remain constant. Once we have the order of the reaction with respect
to each reactant, we can write the rate-law expression. To calculate the rate constant for the reaction, we
can rearrange the rate law to solve for k and use the data from any of the experiments. Finally we can
calculate the rate of the formation of a product from the concentrations of the reactants by substituting
those concentrations and the calculated value of k into the rate-law expression, making sure the result
agrees with the stoichiometry of the reaction.
Solve
(a) Using experiments 1 and 2, we find that the order of the reaction with respect to CO is 0:
æ öx
rate 2 çç[CO ]0,2 ÷ ÷
=ç ÷
rate1 ççè [CO ]0,1 ø÷
÷
1.44´ 10- 5 M /s æ öx
= çç 0.413 M ÷
÷
1.44´ 10- 5 M /s çè 0.826 M ÷ø
1.00 = 0.500 x
x= 0
Using experiments 2 and 3, we find that the order of the reaction with respect to NO2 is 2:
æ öx
rate3 çç[NO 2 ]0,3 ÷÷
=ç ÷
rate2 ççè[NO 2 ]0,2 ÷
÷
ø
5.76´ 10- 5 M /s æ öx
= çç 0.526 M ÷
÷
1.44´ 10- 5 M /s çè 0.263 M ÷ø
4.00 = 2.00 x
x= 2
The rate law for this reaction is Rate = k[CO]0[NO2]2 = k[NO2]2.
(b) Rearranging the rate-law expression to solve for k and using the data from experiment 1 give
rate 1.44´ 10- 5 M /s

k= 2
= 2
= 2.08´ 10- 4 M - 1 ×s- 1
[NO2 ] (0.263 M )
(c) The rate of formation of CO2 when [NO2] = [CO] = 0.500 M is
2.08´ 10- 4
Rate = ´ (0.500 M ) 2 = 5.20´ 10- 5 M /s
M ×s
Think About It
Because the concentration of CO has no effect on the rate of the reaction, [CO] has an exponent of zero and
the carbon monoxide concentration does not appear in the rate-law expression.

Using the data provided, we may calculate the average rates of consumption of HCN and acetaldehyde
between 11.12 and 40.35 minutes.
Analyze
The average rate of consumption is given by the expression
 [reactant ]
Rate =
t
We may calculate the individual rates by finding the difference in the concentration of each reactant at
40.35 minutes and 11.12 minutes.
Solve
(a) The rate of consumption of HCN is
0.0515 M - 0.0619 M
Rate = = - 3.56´ 10- 4 M /min
40.35 min - 11.12 min
(b) The rate of consumption of acetaldehyde is
0.0242 M - 0.0346 M
Rate = = - 3.56´ 10- 4 M /min
40.35 min - 11.12 min
Think About It
The rate of consumption of both reactants is the same, suggesting that each reactant has an equal order in
the reaction.

From the data given for the concentration of ClOO over time as it decomposes to Cl 2 and O2, we are to
determine the rate law and calculate the value of k for this reaction.
Analyze
We are given a single data set. If a plot of [ClOO] versus time yields a straight line, then the reaction is
zero order with respect to ClOO. If the plot of ln[ClOO] versus time yields a straight line, then the reaction
is first order with respect to ClOO. If a plot of 1/[ClOO] versus time yields a straight line, then the reaction
is second order with respect to ClOO. The slope of the line on the appropriate graph gives the rate constant
k for the reaction (slope = −k for a zero- or first-order reaction and slope = +k for a second-order reaction).
Solve
The rate law is Rate = k[ClOO].
92 | Chapter 13
The first-order plot is linear with the slope = −k = −3.0, so k = 3.0 s−1.
Think About It
The half-life of this first-order reaction is
0.693 0.693
t1/ 2 = = = 0.23 s
k 3.0 s- 1

For the first-order decomposition of H2O2 in the presence of Fe3+, the reaction proceeds with a half-life of
17.3 minutes. Using this data, we may calculate the concentration of H 2O2 remaining after 10.0 minutes.
Analyze
The half-life for a first-order reaction is given by the equation
0.693
t1/ 2 =
k
Substituting in the value for the half-life will allow us to solve for the rate constant, k. Given that the initial
concentration of H2O2 ([H2O2]0) is 0.437 M, the rate constant may then be used to determine the
concentration at 10.0 minutes ([H2O2]t) using the integrated rate law for a first-order reaction:
æ[H 2O 2 ] ö
ç t ÷
÷
ln çç ÷
÷ = - kt
çè[H 2O 2 ]0 ø
÷
Since this time is less than one half-life, it is reasonable to expect that the concentration of H 2O2 will be
slightly more than half of the original value.
Solve
The rate constant for this reaction is
0.693 0.693
k= = = 0.04006 min - 1
t1/ 2 17.3 min
Solving for the concentration of H2O2 after 10 minutes:

æ[H 2O 2 ] ÷ö
ln ççç t ÷
÷ = - 0.04006 min - 1 (10.0 min )
çè 0.437 M ø÷
[H 2O2 ]t
= e- 0.4006
0.437 M
[H 2O2 ]t = 0.293 M
Think About It
Our initial guess seems accurate: the concentration is approximately 67% of its initial value.

Given the half-life (45 days) for a particular yogurt, we may calculate the estimated “shelf life” before the
product has only 80% of its initial quality.
Analyze
For this question, we will treat “quality” as if it were a defined chemical species (X) decaying in a first-
order fashion. The half-life for a first-order reaction is given by the equation
0.693
t1/ 2 =
k
Substituting in the value for the half-life will allow us to solve for the rate constant, k. Given that the
acceptable ratio of quality at time of sale ([X]t) to initial quality ([X]0) is 80% (or 0.80), the rate constant may
then be used to determine the maximum amount of time elapsed since manufacture using the first-order
equation
æ[X ] ÷ ö
ç
ln çç t ÷ ÷ = - kt
çè[X ]0 ÷
÷
ø
When rounding the number of days for the “best before” statement, we should round down, to ensure that
customers buying yogurt at the end of the day do not receive inferior product.
Solve
The rate constant for this reaction is
0.693 0.693
k= = = 0.00154 d- 1
t1/ 2 45 days
Solving for the maximum amount of time elapsed since manufacture:

æ0.80 ÷
ö
ln çç ÷= - 0.0154 d ´ t
÷
- 1
çè 1 ø
t = 14.5 days
The maximum shelf life of the yogurt should be 14 days.
Think About It
By the end of the fourteenth day, customers would be purchasing yogurt that is 79% of its initial quality.

94 | Chapter 13
For the first-order decomposition of acetoacetic acid, we must determine the rate constant, considering the
half-life is 139 minutes. Given an initial concentration of acetoacetic acid, we must also calculate the
concentration after 5 hours have elapsed.
Analyze
The half-life for a first-order reaction is given by the equation
0.693
t1/ 2 =
k
Substituting in the value for the half-life will allow us to solve for the rate constant, k. Given that the initial
concentration of acetoacetic acid ([HAA]0) is 2.75 M, the rate constant may then be used to determine the
concentration at 5 hours (18,000 s, [HAA]t) using the integrated rate law for a first-order reaction:
æ[HAA ] ÷ ö
ç t ÷
ln çç ÷ = - kt
çè[HAA ]0 ÷
÷
ø
Since this time is just over two half-lives, it is reasonable to expect that the concentration of H 2O2 will be
slightly less than a quarter of the original value.
Solve
(a) The rate constant for this reaction is
0.693 0.693 1 min
k= = ´ = 8.31´ 10- 5 s- 1
t1/ 2 139 min 60 s
(b) Solving for the concentration of acetoacetic acid after 5 hours:
ln ([X ]t ) = - kt + ln ([X ]0 )
ln ([X ]t ) = - 8.31´ 10- 5 s- 1 (18, 000 s )+ ln (2.75 M )
[X ]t = e- 0.4842
[X ]t = 0.616 M
Think About It
Our initial guess was accurate: the concentration of acetoacetic acid after 5 hours will be just over 22% of
the original concentration.

Given the rate constant for a second-order reaction, we may determine the half-life of the reactant. Given
an initial and final concentration, we may also determine the time elapsed.
Analyze
The half-life for a second-order reaction is given by the equation
1
t1/ 2 =
k [X ]0
Given that the initial concentration of p-toluenesulfinic acid ([X]0) is 0.355 M, the rate constant may then
be used to determine the time taken to reach a concentration ([X] t) of 0.0355 M using the integrated rate
law for a second-order reaction:
1 1
kt = -
[X ]t [X ]0
Solve
(a) The half-life for this equation and concentration is
1
t1/ 2 = - 1
= 20.0 min
0.141 M min- 1 (0.355 M )
(b) The time required to reach a concentration of 0.0355 M is

1 1
(0.141 M - 1 min- 1 )t = -
0.0355 M 0.355 M
t = 180 min
It will take three hours for the concentration of p-toluenesulfinic acid to reach 0.0355 M.
Think About It
Unlike a first-order reaction, the second-order reaction described in this problem has a half-life that
depends on the initial concentration of reactant.

For the decomposition reaction of N2O to N2 and O2, we are to write the rate law if the plot of ln[N 2O]
versus time is linear and then determine the number of half-lives it would take for the concentration of N2O
to become 6.25% of its original concentration.
Analyze
The integrated rate laws for zero-, first-, and second-order reactions with their half-life equations are as
follows:
[A] = −kt + [A]0 zero order t1/2 = [A]0/2k
ln[A] = −kt + ln[A]0 first order t1/2 = 0.693/k
1/[A] = kt + 1/[A]0 second order t1/2 = 1/k[A]0
Solve
(a) Given that the plot of ln[N2O] versus time is linear, the reaction is first order with respect to N 2O, and
the rate law is Rate = k[N2O].
(b) The number of half-lives needed to reduce the concentration to 6.25% would be, where n = number of
half-lives,
6.25
= 0.50n
100
0.625 = 0.50n
ln(0.0625) = n ln(0.50)
n= 4
Think About It
The number of half-lives needed to reduce the concentration of a reactant to a certain amount of product is
not dependent on the order of the reaction or on the magnitude of the rate constant.

96 | Chapter 13
From the information given about the linearity of the plots of [C 4H6], ln[C4H6], and 1/[C4H6] versus time,
we can determine the rate law for the dimerization of C 4H6 and then calculate the number of half-lives
required for the concentration of C4H6 to be reduced to 3.1% of its original concentration.
Analyze
The integrated rate laws for zero-, first-, and second-order reactions with their half-life equations are as
follows:
[A] = −kt + [A]0 zero order t1/2 = [A]0/2k
ln[A] = −kt + ln[A]0 first order t1/2 = 0.693/k
1/[A] = kt + 1/[A]0 second order t1/2 = 1/k[A]0
Solve
(a) Since we are given that the plot of 1/[C4H6] versus time is linear, the reaction is second order with
respect to C4H6, and the rate law is Rate = k[C4H6]2.
(b) The number of half-lives (n) needed to reduce the concentration of C4H6 to 3.1% is
6.1
= 0.50n
100
0.031 = 0.50n
ln(0.031) = n ln(0.50)
n= 5
Think About It
The number of half-lives needed to reduce the concentration of a reactant to a certain amount is not
dependent on the order of the reaction or on the magnitude of the rate constant.

From the data given for the concentration of 32P over time, we are to determine the rate law, calculate the
value for k, and determine the half-life for this radioactive decay.
Analyze
Radioactive decay follows first-order kinetics. This is confirmed in part (b), where we are told to determine
the first-order rate constant. A plot of ln[32P] versus time for this decay gives a straight line with
slope = −k. The half-life of a first-order decay is given by
0.693
t1/ 2 =
k
Solve
(a) First-order plot for Problem 14.73:
The rate law for this radioactive decay is Rate = k[32P].

(b) k = −slope = 0.0485 day−1
0.693
(c) t1/ 2 = - = 14.3 days
0.0485 day 1
Think About It
The time needed for [32P] to reduce to 1.00% of its original concentration, where n = number of half-lives, is
1.00
= 0.50n
100
0.0100 = 0.50n
ln(0.0100) = n ln(0.50)
n = 6.64 half lives
The number of days is n  t1/2 = 6.64  14.3 days = 95 days.

From the data given for the second-order decomposition of HNO2 to NO, NO2, and H2O, we are to
calculate the value of k and the half-life for this reaction.
Analyze
Because this reaction is second order in HNO2, when we plot the concentration of HNO2 versus time
according to the second-order integrated rate equation
1/[A] = kt + 1/[A]0
the slope of the line is equal to k and the half-life will be t1/2 = 1/k[A]0.
Solve
(a) The rate law for this second-order reaction is Rate = k[HNO2]2. A plot of the reciprocal of concentration
of HNO2 versus time for this second-order reaction gives the slope = k = 4.097  10−4 M−1 min−1.
(b) The half-life of this reaction is

1 1
t1/2 = = = 1.565´ 104 min or 10.87 d
k [A ]0 (4.097´ 10 Μ min- 1 )(0.1560 Μ )
- 4 - 1
Think About It
The half-life of a second-order reaction decreases as the initial concentration of the reactant increases. For
an initial concentration of 0.312 M for this particular reaction, the half-life is
98 | Chapter 13
1 1
t1/2 = = = 7.823´ 103 min or 5.433 d
k [A ]0 (4.097´ 10- 4 Μ - 1 min- 1 )(0.3120 Μ )

Given that the dimerization of ClO to Cl2O2 is second order with respect to ClO, we are to determine the
value of the rate constant and calculate the half-life of this reaction.
Analyze
We are given a single data set and that the reaction is second order. For this second-order reaction, a plot of
1/[ClO] versus time gives a straight line with a slope equal to k, the reaction rate constant. The half-life of
this second-order reaction is
1
t1/ 2 =
k [ClO]0
where [ClO]0 is the initial concentration of ClO used in the reaction.
Solve
The value of k for this reaction is k = slope = 5.40  10−12 cm3/(molecules  s), and the half-life of the
reaction is as follows:
1 1
t1/ 2 = = = 0.712 s
k [ClO]0 æçç 5.40 ´ 10- 12
cm 3 öæ
÷ç 2.60 ´ 1011 molecules ö
÷
÷
÷ç ÷
÷
ççè molecules ×s øè ÷çç 1 cm3 ÷
ø
Think About It
For a second-order reaction, as we increase the initial concentration of the reactant, the half-life gets
shorter.

From the data given for the concentration of Cl 2O2 over time as it decomposes to ClO and the fact that the
reaction is first order, we can calculate the rate constant and the half-life for the reaction.
Analyze
For a first-order reaction, the slope of the line of the linear plot of ln[A] versus time equals −k. Once we
have the value of k, the half-life may be calculated by
0.693
t1/ 2 =
k
Solve
Because the slope = −8.72  10−4, k = 8.72  10−4 s−1. The half-life of the reaction is
0.693
t1/ 2 = = 795 s
8.72´ 10- 4 s- 1
Think About It
From this information we could calculate how long it might take, for example, for the concentration of
Cl2O2 to decrease to 15% of its original concentration. The integrated rate law for first-order reactions is
ln[A] = −kt + ln[A]0
where [A] = 15 M, [A]0 = 100 M, and k = 8.715  10−4 s−1:
ln(15) = −(8.715  10−4 s−1  t) + ln(100)
t = 2.18  103 s
We are asked to consider the size of the activation energy in the forward and reverse directions for a
reaction in which the reactants have a higher energy than the products.
Analyze
The reaction described in this problem is exothermic, with the difference in energy between the high-energy
reactants and the lower-energy products being released as heat. The activation barriers for these two
processes are shown in the diagram.
100 | Chapter 13
Solve
Ea is higher in the reverse direction.
Think About It
For an endothermic reaction, the opposite trend is true.

We are to explain why the rate of reaction increases at higher temperatures, though the rate law does not
include the term T.
Analyze
Consider the components of the rate law
rate = k[A]
If the rate of reaction is increasing with temperature, either the concentration [A] or the rate constant k must
also be increasing. If we assume the concentration of reactants stays approximately the same, the rate
constant must be the cause of the increase in the rate of reaction. The rate constant is described by the
Arrhenius equation:
k = Ae- Ea /RT
Solve
Although it does not at first glance appear that T is contained in the rate law, the value of k changes with T,
as described by the Arrhenius equation. As the temperature increases, the rate constant increases, leading to
an increase in the rate of reaction.
Think About It
Combining the rate law and Arrhenius equation helps to demonstrate the dependence of rate on T:
rate = (Ae- Ea /RT

)[A]
Note that the two A terms are different. One is the pre-exponential factor, and the other is a placeholder for
a reactant.

We are to explain why the order of a reaction is independent of temperature, yet the value of k changes with
temperature.
Analyze
We need to consider how temperature affects the motion and collision of the reactants.
Solve
An increase in temperature increases the frequency and the kinetic energy at which the reactants collide.
This speeds up the reaction, changing the value of k. The activation energy of the slowest step in the
reaction, however, is not affected by a change in temperature, and, therefore, the order of the reaction is
unaffected.
Think About It
As a general empirical observation, heating a reaction by 10C doubles the rate of reaction.

By looking at the Arrhenius equation, we can determine if Ea depends on temperature.
Analyze
The Arrhenius equation is
Ea
ln k = ln A -
RT
Solve
No. From the form of the equation, we see a dependence of k on temperature because the equation is in the
form of y = mx + b where y = ln k, and x = 1/T. It is the rate constant, not Ea, that changes with temperature.
Think About It
The Arrhenius equation was actually first proposed by Jacobus van’t Hoff, but it was Svante Arrhenius who
interpreted it and introduced the idea of an activation energy.

In comparing two first-order reactions with different activation energies, we are to decide which would
show a larger increase in its rate as the reaction temperature is increased.
Analyze
We can use the Arrhenius equation to mathematically determine which reaction would be most accelerated
by an increase in temperature:
Ea
ln k = ln A -
RT
Solve
Let’s assume that T2 = 2T1. For either reaction, the difference in their rate constants is as follows:
Ea Ea
ln kT1 = ln A - ln kT2 = ln A -
RT1 RT2
- Ea E E æ1 1 ö ÷
ln kT2 - ln kT1 = + a = a çç - ÷
÷
RT2 RT1 R çèT1 T2 ø
But since T2 = 2T1,
Ea æ ö
çç 1 - 1 ÷ Ea
ln kT2 - ln kT1 = ÷
÷ =
R çèT1 2T1 ø 2 RT1
For Ea = 150 kJ/mol,

150 kJ/mol
ln kT2 - ln kT1 =
2 RT1
For Ea = 15 kJ/mol,
15 kJ/mol
ln kT2 - ln kT1 =
2 RT1
Comparing these as a ratio,

102 | Chapter 13
150 kJ/mol
ln kT2 - ln kT1 (for Ea = 150 kJ/mol) 2 RT1
= = 10
ln kT2 - ln kT1 (for Ea = 15 kJ/mol) 15 kJ/mol
2 RT1
Therefore, the reaction with the larger activation energy (150 kJ/mol) would be accelerated more than the
reaction with the lower activation energy (15 kJ/mol) when heated.
Think About It
Our derivation demonstrates that different reactions with different activation energies will not accelerate in
the same way when they are heated.

We are asked to explain why a reaction with a small activation energy also has a rate constant that changes
dramatically with the temperature.
Analyze
The equation that relates the rate constant, k, with the temperature, T, is the Arrhenius equation:
Ea
ln k = ln A -
RT
Solve
Since Ea is small and R is a constant, changes to T will dominate the Ea /RT term in this equation. In light of
this relationship, it makes sense that large changes to T will cause a large change to k.
Think About It
The opposite situation is also true: a reaction with a large value for the Ea will have a rate constant that does
not change as dramatically with changes in temperature.

Considering the two plots, we are asked to identify which has a greater activation energy.
Analyze
The y-axis for this plot is ln K, while the x-axis for this plot is 1/T. These variables are present in the
Arrhenius equation in the form
Ea æ ö
çç 1 ÷
ln k = -
ç ÷
÷+ ln A
R èT ø
Considering this equation, the y-intercept of these plots will be equal to ln A, while the slope will be equal
to −Ea/R. The plot with the most negative slope will have the largest value of Ea.
Solve
Reaction 2 (the red line) has the most negative slope and thus the largest Ea.
Think About It
The point at which the two lines intersect tells us the temperature at which the rate constants for these two
reactions will be equal.

Considering the two plots, we are asked to identify which is more sensitive to temperature change.
Analyze
The equation that relates the rate constant, k, with the temperature, T, is the Arrhenius equation:
Ea
ln k = ln A -
RT
The reaction with the smallest Ea will experience the greatest difference in k as the temperature changes. As
discussed in Problem 13.83, the plot with the most negative slope will have the largest value of Ea.
Solve
The plot with the least negative slope and thus the smaller Ea and greater variation in k as the temperature
changes is reaction 1 (the blue line).
Think About It
Although the red line (reaction 2) has a greater slope than the blue line (reaction 1), recall that this is not a
plot of k vs. T, but ln k vs. 1/T. If you had assumed a greater slope meant that the reaction was more
sensitive to a change in temperature, you would have selected the wrong line!

We can use an Arrhenius plot of rate constant versus temperature for the reaction of O and O 3 to determine
the activation energy (Ea) and the value of the frequency factor (A).
Analyze
Ea æ ö
çç 1 ÷
ln k = - ÷
÷+ ln A
R çèT ø
If we plot ln k ( y-axis) versus 1/T (x-axis), we obtain a straight line with slope m = −Ea /R. The activation
energy is therefore calculated by
Ea = −slope  R
where R = 8.314 J/(mol  K). The y-intercept (b) is equal to ln A, so we can calculate the frequency factor
by b = ln A or eb = A.
Solve
The Arrhenius plot gives a slope of m = −2060 and a y-intercept of b = 0.00160.
Ea = −[−2060 K  8.314 J/(mol  K)] = 1.713  104 J/mol or 17.1 kJ/mol

104 | Chapter 13
b = 0.00160 = ln A
A = e0.00160 = 1.002
Think About It
Once we have the values of Ea and A from the plot, we can calculate the value of k at any temperature.

We can use an Arrhenius plot of rate constant versus temperature for the reaction of NO 2 and O3 to
determine the activation energy (Ea) and to find the rate constant for the reaction at 300 K.
Analyze
Ea æ ö
çç 1 ÷
ln k = -
ç ÷
÷+ ln A
R èT ø
If we plot ln k ( y-axis) versus 1/T (x-axis), we obtain a straight line with slope m = −Ea/R. The activation
Ea = −slope  R
by b = ln A or eb = A. Once Ea and A are known, we may use another form of the Arrhenius equation to
calculate k at any temperature:
k = Ae- Ea /RT
Solve
The Arrhenius plot gives a slope of m = −2450.6 and a y-intercept of b = 25.005.
(a) Ea = −[−2450.6 K  8.314 J/(mol  K)] = 2.04  104 J/mol or 20.4 kJ/mol
(b) To calculate k at 300 K, we first need the value of A:
A = e25.005 = 7.237  1010
The value of k at 300 K is
æ
çç 2.04´ 104 J/mol ö
÷
ç ÷
÷
÷
10 ççè8.314 J ×mol ×K (300 K) ÷
- 1 - 1
ø
k = 7.237 ´ 10 e
k = 2.03´ 107 M - 1 s- 1
Think About It
Alternatively, k can be calculated from the original Arrhenius equation:
Ea
ln k = - + ln A
RT
- 2.04´ 104 J/mol
ln k = + 25.005 = 16.83
8.314 J ×mol- 1 ×K - 1 (300 K)
k = 2.03´ 107 M - 1 s- 1

We can use an Arrhenius plot of rate constant versus temperature for the reaction of N 2 with O2 to form NO
to determine the activation energy (Ea), the frequency factor (A), and the rate constant for the reaction at
300 K.
Analyze
Ea æ ö
çç 1 ÷
ln k = - ÷
÷+ ln A
R çèT ø
Ea = −slope  R
k = Ae- Ea /RT
Solve
The Arrhenius plot gives a slope of m = −37,758 and a y-intercept of b = 24.641.
(a) Ea = −[−37,758 K  8.314 J/(mol  K)] = 3.14  105 J/mol or 314 kJ/mol
(b) A = e24.641 = 5.03  1010
æ
çç 3.14´ 105 J/mol ö
÷
çç ÷
÷
÷
÷
10 çè8.314 J ×mol ×K (300 K) ø
- 1 - 1
(c) k = 5.03´ 10 e = 1.06´ 10- 44 M - 1/2 s- 1
106 | Chapter 13
Think About It
Alternatively, k can be calculated from the original Arrhenius equation:
Ea
ln k = - + ln A
RT
- 3.14´ 105 J/mol
ln k = + 24.641 = - 101.25
8.314 J ×mol- 1 ×K - 1 (300 K)
k = 1.06´ 10- 44 M - 1/ 2 s- 1

We can use an Arrhenius plot of rate constant versus temperature for the decomposition of N2O5 to
determine the activation energy (Ea) and the rate constant for the reaction at 300 K.
Analyze
Ea æ ö
çç 1 ÷
ln k = -
ç ÷
÷+ ln A
R Tøè
Ea = −slope  R
k = Ae- Ea /RT
Solve
The Arrhenius plot gives a slope of m = −11,781 and a y-intercept of b = 30.164.
(a) Ea = −[−11,781 K  8.314 J/(mol  K)] = 9.79  104 J/mol or 97.9 kJ/mol
(b) To calculate k at 300 K we first need the value of A:
A = e30.164 = 1.26  1013
The value of k at 300 K is

æ 9.79´ 104 J/mol ö÷

ççç ÷
÷
ç ÷
13 èç8.314 J ×mol ×K (300 K) ø÷
- 1 - 1
k = 1.26´ 10 e = 1.13´ 10- 4 s- 1
Think About It
This reaction will be relatively slow since k  1.

We can use an Arrhenius plot of rate constant versus temperature for the reaction of ClO 2 and O3 to
determine the activation energy (Ea) and the value of the frequency factor (A).
Analyze
Ea æ ö
çç 1 ÷
ln k = -
ç ÷
÷+ ln A
R èT ø
Ea = −slope  R
by b = ln A or eb = A.
Solve
Ea = −[−4698.7 K  8.314 J/(mol  K)] = 3.91  104 J/mol or 39.1 kJ/mol

b = 27.872 = ln A
A = e27.872 = 1.27  1012
Think About It
Once we have the values of Ea and A from the plot, we can calculate the value of k at any temperature.

108 | Chapter 13
Given the value of the rate constant for the reaction of Cl with CH 4 to form HCl and CH3 at 298 K and at
three additional temperatures, we can use an Arrhenius plot to calculate the activation energy (Ea) and the
frequency factor (A) for the reaction.
Analyze
Ea æ ö
çç 1 ÷
ln k = - ÷
÷+ ln A
R çèT ø
Ea = −slope  R
using b = ln A or eb = A.
Solve
Ea = −[−1387.5 K  8.314 J/(mol  K)] = 1.15  104 J/mol or 11.5 kJ/mol

A = e22.567 = 6.32  109
Think About It
The rate constant for this reaction is fairly large, so we expect that the reaction will proceed quickly to
products.

We are asked if the reaction between NO and Cl2 could occur in one step, given that the reaction is first
order in each reactant.
Analyze
If the reaction were to occur in one step, a NO molecule would have to collide with a Cl2 molecule to form
the activated complex, and onward to the products. A reaction involving multiple steps still requires that
the molecularity of the rate-determining (slow) step be equal to the order of the reaction.
Solve
While it is possible for the reaction to occur in one step, it is not necessarily true. It is possible for a
reaction that is first order in each reactant to proceed via a multistep process in which the rate-determining
step is monomolecular in NO and Cl2.
Think About It
The reaction sequence and number of steps taken to form a product are known as the reaction mechanism.
Chemists will often propose a mechanism, then seek experimental confirmation of their proposal.

We are asked if the reaction between NO and H2 could occur in one step, given that the reaction is second
order in NO.
Analyze
If the reaction were to occur in one step, a NO molecule would have to collide with a H 2 molecule to form
the activated complex, and onward to the products. A reaction involving multiple steps still requires that
the molecularity of the rate-determining (slow) step be equal to the order of the reaction.
Solve
This reaction cannot occur in one step and be second order with respect to NO. The rate-determining step in
this reaction involves a collision between two NO molecules, forming an activated complex that proceeds
to react with H2 in subsequent fast steps.
Think About It
One possible mechanism for this reaction is
NO(g) + NO(g) → N2O4(g) (slow)
N2O4(g) + H2(g) → 2 HNO(g) (fast)

For a reaction that is first order in A (the only reactant), we are asked to determine if it must proceed in
only one step.
Analyze
The molecularity of an elementary step dictates the order of the reaction in that reactant. If the reaction
does proceed in one step that is first order in A, the overall rate law will be first order in A.
Solve
The statement provided might be true, but does not necessarily have to be true. It is possible that the
reaction could proceed in multiple steps, with a rate-determining step that is first order in A. For example:
A→C (slow)
C→B (fast)
This mechanism proceeds in two steps, but would be expected to be first order in A only.
Think About It
A reaction with a short-lived intermediate, such as that described above, might appear to proceed in one
step. Careful measurement is required to determine if such an intermediate is formed.

110 | Chapter 13
For a reaction that is zero order in a reactant, we are to determine if that means the reactant is not involved
in any collisions with other reactants during the course of the reaction.
Analyze
When a reactant is zero order, it does not appear in the overall rate equation.
Solve
No. The reactant may still be used and therefore must collide with other reactants, but it is not involved in
the rate-determining step of the reaction.
Think About It
The rate law only expresses the concentration dependence of those reactants (and intermediates) involved
in the slowest (rate-determining) step of the mechanism.

Given some information about the molecularity of a two-step reaction, we may sketch a reaction coordinate
diagram illustrating the energy of the reactants, products, intermediates, transition states, and activation
energies.
Analyze
The first step is a slow (rate-determining) conversion of A to B:
A→B (slow)
The second step is a fast decomposition of B into C and D:
B→C+D (fast)
The decomposition suggests that each step in the reaction is exothermic (lower in energy than the starting
material). Slower steps will have a higher activation energy, so the first transition state should have the
highest energy in the diagram.
Solve
Think About It
The relative energies of A, B, and C + D are approximate in this diagram, as are the activation energies. We
could determine these values experimentally and modify the diagram to reflect these findings.

Given some information about the molecularity of a two-step reaction, we may sketch a reaction coordinate
diagram illustrating the energy of the reactants, products, intermediates, transition states, and activation
energies.
Analyze
The first step is a fast conversion of A to B:
A→B (fast)
The second step is a slow (rate-determining) decomposition of B into C and D:
B→C+D (slow)
The decomposition suggests that each step in the reaction is exothermic (lower in energy than the starting
material). Slower steps will have a higher activation energy, so the second transition state should have the
highest energy in the diagram.
Solve
Think About It
Notice that while the energies of A, B, and C + D are the same as those in Problem 13.95, the activation
barriers are different. While the kinetics of these two reactions are different, the thermodynamic energies
are not!

For each of the elementary steps given, we are to write the rate law and determine whether the step is uni-,
bi- or termolecular.
Analyze
The rate law for an elementary step in a mechanism is written in the form
Rate = k[A]x[B]y[C]z
112 | Chapter 13
where A, B, and C are the reactants involved in the elementary reaction and x, y, and z are the
stoichiometric coefficients for the respective reactants in the elementary reaction.
Solve
(a) Rate = k[SO2Cl2]. Because this elementary step involves only a molecule of SO2Cl2, it is unimolecular.
(b) Rate = k[NO2][CO]. Because this elementary step involves a molecule of NO 2 and a molecule of CO, it
is bimolecular.
(c) Rate = k[NO2]2. Because this elementary step involves two molecules of NO2, it is bimolecular.
Think About It
Termolecular elementary reactions are rare.

For each of the elementary steps given, we are to write the rate law and determine whether the step is uni-,
bi-, or termolecular.
Analyze
The rate law for an elementary step in a mechanism is written in the form
Rate = k[A]x[B]y[C]z
where A, B, and C are the reactants involved in the elementary reaction and x, y, and z are the
stoichiometric coefficients for the respective reactants in the elementary reaction.
Solve
(a) Rate = k[Cl][O3]. Because this elementary step involves a Cl atom and an O3 molecule, it is
bimolecular.
(b) Rate = k[NO2]2. Because this elementary step involves two NO2 molecules, it is bimolecular.
(c) Rate = k[14C]. Because this elementary step involves only a 14C atom, it is unimolecular.
Think About It
Termolecular elementary reactions are rare, as they require three species to collide with the correct
orientation and energy.

From three elementary steps that describe a reaction mechanism, we are to write the overall chemical
equation.
Analyze
To write the overall chemical reaction, we need to add the elementary steps, being sure to cancel the
intermediates in the reaction.
Solve
N 2O5 ( g ) → NO3 ( g ) + NO 2 ( g )
NO3 ( g ) → NO 2 ( g ) + O(g)
2 O(g ) → O 2 ( g )
N 2O5 ( g ) + O( g ) → 2 NO 2 ( g ) + O 2 ( g )
Think About It
In this reaction, NO3 is a reaction intermediate. It is generated in the reaction but consumed in a subsequent
step in the mechanism.

From three elementary steps that describe a reaction mechanism, we are to write the overall chemical
equation.
Analyze
To write the overall chemical reaction, we need to add the elementary steps, being sure to cancel the
intermediates in the reaction.
Solve
ClO- (aq) + H 2O( ) → HClO(aq) + OH- (aq)
I- (aq) + HClO(aq) → HIO(aq) + Cl- (aq)
OH- (aq) + HIO(aq) → H 2O( ) + IO- (aq)
ClO- (aq) + I- (aq) → Cl- (aq) + IO- (aq)
Think About It
In this reaction, HClO, OH−, and HIO are reaction intermediates. They are generated in the reaction but
consumed in subsequent steps in the mechanism.

We are given the mechanism by which N2 reacts with O2 to form NO. For a given rate law of
Rate = k[N2][O2]1/2
we are to determine which step in the mechanism is the rate-determining step.
Analyze
To determine which step in the proposed mechanism might be the slowest, we can write the rate law for the
mechanism when the first, second, or third step is slow and then match the theoretical rate law to the
experimental rate law.
Solve
If the first step is slow, the rate law is
Rate = k1[O2]
This does not match the experimental rate law, so the first step is not the slowest step in the mechanism.
If the second step is slow, then the rate law is
Rate = k2[O][N2]
Because O is an intermediate, we use the first step to express its concentration in terms of concentrations of
the reactants. For a fast step occurring before a slow step in a mechanism,
Rateforward = Ratereverse
k1[O2] = k−1[O]2
Rearranging to solve for [O],

114 | Chapter 13
1/ 2
æ k1 ö
÷
ç
[O]= çç [O2 ]÷÷
è k- 1 ø
Substituting this into the rate law from the second step gives
æk ö1/2
Rate = k2 çç 1 [O2 ]÷
1/2
÷
÷ [N 2 ]= k [O 2 ] [N 2 ]
çè k- 1 ø
This rate law matches the experimental rate law, so the rate-determining step is the second step.
We should check to see if the mechanism of the third step is the slow step and might also give the
experimental rate law. Following the logic above,
Rate = k3[N][O]
From the second fast step in the mechanism,
k2[O][N2] = k−2[NO][N]
Solving for [N], an intermediate, gives
k2 [O][N 2 ]
[N]=
k- 2 [NO]
From the first fast step in the mechanism,

k1[O2] = k−1[O]2
Solving for [O]2 gives
2 k1
[O ] = [O 2 ]
k- 1
Substituting these expressions into the rate law from the third step in the mechanism gives
k æ[O 2 ][N 2 ]÷
ö k [O 2 ][N 2 ]
´ 1 ççç
k2 ÷
Rate = k3 ´ ÷=
k- 2 k- 1 çè [NO ] ø ÷ [NO]
This rate law does not match the experimental rate law, so our earlier finding that the second step was rate
determining was correct.
Think About It
Just because the rate law for a mechanism matches the experimental rate law does not mean that
mechanism is the mechanism. Another mechanism might also give the same experimental rate law.

Given a proposed mechanism for the decomposition of H2O2, we are to determine which step is the rate-
determining (slow) step if the reaction is known by experiment to be first order in H 2O2.
Analyze
The slowest step in a mechanism determines the rate law. From each elementary reaction we can write a
rate-law expression.
Solve
If the first step is the rate-determining step, the rate law is
Rate = k1[H2O2]
This is consistent with the reaction being first order in the concentration of H 2O2, so the first step is likely
to be the rate-determining step.
Think About It
If the second step were rate determining, the rate law would be
Rate = k2[H2O2][OH]
This is first order in H2O2 but is also first order in OH concentration. OH in this reaction is a reaction
intermediate. Because the first step is fast and reversible, we can write
kf[H2O2] = kr[OH]2
Rearranging this to solve for the concentration of OH, the reaction intermediate, gives
æk ö1/ 2
[OH ]= ççç f [H 2O2 ]÷÷÷
è kr ø
Substituting this concentration of OH into the rate-law expression for the rate-determining step gives
æk ö1/2 ækf ö 1/2
Rate = k2 [H 2O2 ]´ çç f [H 2O2 ]÷ ç ÷ 3/2

÷
÷ = k 2ç ÷
÷ [H 2O2 ]
çè kr ø èç kr ø
So, the rate law derived from the mechanism where the second step is rate determining is inconsistent with
the experimentally observed rate law.

We are given the mechanism by which NO reacts with Cl2 to produce NOCl2. For a given rate law of
Rate = k[NO][Cl2]
we are to determine which step in the mechanism is the rate-determining step.
Analyze
To determine which step in the proposed mechanism might be the slowest, we can write the rate law for the
mechanism when the first, second, or third step is slow and then match the rate law to the experimental
rate law.
Solve
If the first step is slow, the rate law is
Rate = k1[NO][Cl2]
This matches the experimental rate law, so the first step is the rate-determining step.
We should check to see if the rate law for the mechanism with the second step as the slow step might also
give the experimental rate law
Rate = k2[NOCl2][NO]
If the second step is slow, then

Rate1 = Rate−1
k1[NO][Cl2] = k−1[NOCl2]
k1
[NOCl2 ]= [NO ][Cl2 ]
k- 1
116 | Chapter 13
Substituting this into the rate-law expression gives

æk ö
÷
Rate = k2 çç 1 [NO ][Cl2 ][
2
÷
÷ NO ]= k [NO ] [Cl2 ]
çè k- 1 ø
This does not match the experimental rate law, so the second step in the mechanism is not the rate-
determining step.
Think About It
Just because the rate law for a mechanism matches the experimental rate law does not mean that
mechanism is the mechanism. Another possible mechanism might also give the same experimental
rate law.

Given a proposed mechanism for the thermal destruction of ozone, we are to consider the relative rates and
reversibility of the elementary steps to determine what properties are consistent with the experimental
observation that the reaction is second order in O3.
Analyze
The rate law is determined by the slowest step in the mechanism. We can write the rate expressions for the
two possibilities—the first step as slow or the second step as slow—and then consider the consistency of
those two possible rate laws with the observation that the reaction is second order in ozone.
Solve
If the first step is slow,
Rate = k[O3]
This is only first order in O3, so the first step as the rate-determining step in the mechanism is inconsistent
with the experimental observation for this reaction.
If the second step is slow, then the first step is fast and reversible, and the rate of the forward reaction is
equal to the rate of the reverse reaction:
kf[O3] = kr[O][O2]
When the second step is rate determining, the rate-law expression will be
Rate = k2[O][O3]
Combining these equations by replacing [O] in the rate-law expression for the second slow step with
kf [O3 ]
[O]=
kr [O2 ]
obtained from the reversible first step of the mechanism gives

2
kf k2 [O3 ]
Rate =
kr [O 2 ]
This rate law is consistent with the observation that the reaction is second order in O 3.
Think About It
The rate law for this reaction also shows an inverse dependence of the reaction rate on the concentration of
O2. This means that if the concentration of O2 increases, the reaction slows down.

From the mechanisms given, we are to determine which are possible for the thermal decomposition of NO 2.
We are given the rate laws for the thermal decomposition reaction, Rate = k[NO2]2.
Analyze
Using the slowest elementary step in the mechanism, we can write the rate-law expression for the
mechanism and then determine if it is consistent with the order of the reaction provided.
Solve
For mechanism (a), the first step in the mechanism is slow, so the rate law is
Rate = k[NO2]
For mechanism (b), the second step in the mechanism is slow, so the rate law is
Rate = k2[N2O4]
Using the first step to express [N2O4] in terms of the concentration of the reactant NO 2 gives
k1[NO2]2 = k−1[N2O4]
k1 2
[N 2O4 ]= [NO2 ]
k- 1
Substituting into the rate expression from the second step,

k2k1 2 2
Rate = [NO 2 ] = k [NO 2 ]
k- 1
For mechanism (c), the first step in the mechanism is slow, so the rate law is
Rate = k[NO2]2
Therefore, mechanisms (b) and (c) are consistent with the thermal decomposition of NO 2.
Think About It
To distinguish between the two possible mechanisms for thermal decomposition, we might try to detect the
different intermediates formed in each. Detection of the formation of N 2O4 would support mechanism (b)
over mechanism (c).

From the possible mechanisms, we are to determine which occurs for the photochemical decomposition of
NO2. We are given that the photochemical decomposition is first order in NO 2.
Analyze
Using the slowest elementary step in the mechanism, we can write the rate-law expression for the
mechanism and then determine if it is consistent with the order of the reaction provided.
Solve
Because the first step in each mechanism is the rate-determining step, the rate laws are as follows:
(a) Rate = k[NO2]2
(b) Rate = k[NO2]2
(c) Rate = k[NO2]
Mechanism (c) is the only first-order rate law, consistent with the photochemical decomposition process.
118 | Chapter 13
Think About It
To distinguish between the two possible mechanisms for thermal decomposition, we might try to detect the
different intermediates formed in each. The detection of N2O4, N2O3, or N2O2 would support mechanism (a),
whereas the detection of NO3 would support mechanism (b).

We are asked if a catalyst affects both the rate and the rate constant of a reaction.
Analyze
A catalyst speeds up a reaction by providing an alternate pathway (mechanism) to the products having a
lower activation energy.
Solve
Yes. Because the rate of the reaction is faster (affecting the rate) and the activation energy is lowered
(affecting the value of k), a catalyst affects both the rate of the reaction and the value of the rate constant.
Think About It
A “negative” catalyst that slows down a reaction would increase Ea and decrease k for a reaction. We call
these “negative catalysts” inhibitors.

We are asked if the rate law for a catalyzed reaction is the same as for the uncatalyzed reaction.
Analyze
A catalyst is used in the reaction but later is regenerated.
Solve
The rate law for a catalyzed reaction, like any other reaction, depends on the species involved in the rate-
limiting step. The rate law for a catalyzed reaction may be the same as the rate law for an uncatalyzed
reaction, but if, for example, the catalyst is involved in the rate-limiting step, then its concentration appears
in the rate law. This pathway, then, would have a different rate law than the uncatalyzed reaction.
Think About It
Remember that catalysts enhance the rate of a reaction by providing a different, lower activation energy
pathway to the products.

We were asked if a substance (catalyst) that increases the rate of a reaction also increases the rate of the
reverse reaction.
Analyze
A catalyst speeds up a reaction by providing an alternate pathway (mechanism) to the products having a
lower activation energy.
Solve
Yes, both the reverse and forward reaction rates are increased when a catalyst is added to a reaction. The
activation energies of both processes are lowered by the different pathway the catalyst provides for the
reaction.
Think About It
Likewise, an inhibitor would decrease the rates of both forward and reverse reactions.

We are asked whether CO is a catalyst in the reaction between NO 2 and CO because it does not appear in
the rate law.
Analyze
A catalyst is used in the reaction but later is regenerated, and a catalyst speeds up a reaction by providing
an alternate pathway (mechanism) to the products having a lower activation energy.
Solve
No. In order to function as a catalyst, the CO would have to speed up the reaction and not be consumed. If
it does not lower the Ea for the reaction and regenerate later in the reaction, it is not a catalyst.
Think About It
The CO may not appear in the rate law because it may not be involved in the rate-limiting step of the
mechanism.

We are to explain why the concentration of a homogeneous catalyst does not appear in the rate law.
Analyze
A catalyst is used in a reaction and later regenerated.
Solve
The concentration of a homogeneous catalyst may not appear in the rate law because the catalyst itself is
not involved in the rate-limiting step.
Think About It
If the catalyst is involved in the slowest step of the mechanism, however, it is involved in the rate law.

We are to identify the better way to determine the rate constant for a slow reaction: adding a catalyst or
increasing the temperature.
Analyze
A catalyst provides a lower activation energy to the reaction through a different mechanism to speed up a
reaction. Heating a reaction causes the reactants to collide more frequently and more effectively without
changing the mechanism.
Solve
It would be best to raise the temperature to determine the rate constant for a slow reaction because the
mechanism for the reaction is not changed.
Think About It
Using the form of Arrhenius’s equation in which we compare two rate constants at two temperatures,
120 | Chapter 13
Ea æ ö
çç 1 ÷
ln k1 = - ÷+ ln A
R èT1 ø÷
ç
Ea æ ö
çç 1 ÷
ln k1 = - ÷+ ln A
R èT2 ø÷
ç
æk ö Ea æ1 1 ö÷
ln k2 - ln k1 = ln çç 2 ÷ ÷= ç - ÷
çè k1 ø÷ R èççT1 T2 ø÷
we could calculate k1 at the lower temperature T1 having measured k2 at the higher temperature T2, and
knowing Ea.

Given the mechanism for the reaction of NO and N 2O to form N2 and O2, we are to determine whether NO
or N2O is used in the reaction as the catalyst.
Analyze
A catalyst is used in a reaction and later regenerated and provides a lower-energy pathway to the products
by lowering the activation energy of the reaction, thereby speeding up the reaction.
Solve
We can assume that the presence of either NO or N2O, if it is a catalyst, increases the rate of the reaction. In
examining the mechanism, we see that N2O is a reactant but does not appear as a product in either reaction.
Thus, N2O is not a catalyst. We also see that NO is present as a reactant and product, thus it is a catalyst
because it is used in the reaction and then regenerated. NO is a catalyst for the decomposition of N 2O.
Think About It
If the slow step of this mechanism were the first step, the rate law would be
Rate = k[NO][N2O]
If the second step were slow, the rate law would be
2 2
[NO] [N 2O]
Rate = k 2
[N 2 ]

Given the mechanism for the destruction of O3 in the presence of NO, we are to explain why NO is
functioning as a catalyst.
Analyze
A catalyst is used in a reaction and later regenerated. It provides a lower-energy pathway to the products by
lowering the activation energy of the reaction, thereby speeding up the reaction.
Solve
NO is used in the reaction in step 1 and regenerated in step 2. So, as long as this mechanism has a lower-
energy pathway to form O2 from O and O3, NO is functioning as a catalyst.
Think About It
If, however, the presence of NO slows down the reaction, it would be an inhibitor.

Using the Arrhenius equation, we can compute and compare the rate constants for the reaction of O 3 with O
versus the reaction of O3 with Cl.
Analyze
We are given values A and Ea for each reaction at 298 K. The Arrhenius equation is
Ea
ln k = - + ln A
RT
Solve
For the reaction of O3 with O,
17.1´ 103 J/mol
ln k = + ln (8.0´ 10- 12 cm3 ×molecule- 1 ×s- 1 )
8.314 J ×mol- 1 ×K- 1 (298 K)
ln k = - 32.45
k = 8.05´ 10- 15 cm3 ×molecule- 1 ×s- 1
For the reaction of O3 with Cl,

- 2.16´ 103 J/mol
8.314 J ×mol- 1 ×K- 1 (298 K)
ln k = - 25.14
k = 1.21´ 10- 11 cm3 ×molecule- 1 ×s- 1
Therefore, the reaction of O3 with Cl has the larger rate constant.
Think About It
Our answer is consistent with a qualitative look at the activation energies and frequency factors for the two
reactions. The higher activation energy and lower frequency factor for the reaction of O 3 with O give a
smaller reaction rate constant.

Using the Arrhenius equation, we can compute and compare the rate constants for the reaction of O 3 with
Cl versus the reaction of O3 with NO.
Analyze
We are given values of A and Ea for each reaction at 298 K. The Arrhenius equation is
Ea
ln k = - + ln A
RT
Solve
For the reaction of O3 with Cl,
- 2.16´ 103 J/mol
8.314 J ×mol- 1 ×K- 1 (298 K)
ln k = - 25.14
k = 1.21´ 10- 11 cm3 ×molecule- 1 ×s- 1
For the reaction of O3 with NO,

122 | Chapter 13
- 11.6´ 103 J/mol

8.314 J ×mol- 1 ×K - 1 (298 K)
ln k = - 31.62
k = 1.85´ 10- 14 cm3 ×molecule- 1 ×s- 1
The reaction with the larger rate constant is the reaction of O3 with Cl.
Think About It
Our answer is consistent with a qualitative look at the activation energies and frequency factors for the two
reactions. The higher activation energy and lower frequency factor for the reaction of O3 with NO give a
smaller reaction rate constant.

We are to explain why a glowing wood splint burns faster in a test tube filled with O 2 than in air.
Analyze
Air is composed of about 21% O2.
Solve
When the concentration of a reactant (O2 for the combustion reaction) increases, the rate of reaction also
increases. As we place the glowing wood in pure O2, the rate of combustion increases.
Think About It
If the wood splint were placed in a test tube filled with argon, the combustion reaction would stop.

We are to explain why a spark is required to initiate the spontaneous combustion of propane in a barbecue
grill.
Analyze
The spark adds energy to the propane–air (oxygen) mixture.
Solve
The spark provides the energy to the propane–air mixture needed to overcome the activation energy barrier
to start the combustion reaction.
Think About It
Once started, the combustion reaction itself is self-sustaining.

We are to explain why a person submerged in cold water is less likely to experience the deleterious
consequences of a lack of oxygen for a given period of time than a person submerged in a warm pool.
Analyze
Chemical reactions are slower at colder temperatures than at warmer temperatures.
Solve
The bodily reactions that use O2 are slower at colder temperatures, so the person submerged in an ice-
covered lake uses less of the already dissolved oxygen in their system than the person in a warm pool.
Think About It
Rapid-cooling technology is being investigated at Argonne National Laboratory for use in surgery patients
and heart attack victims to reduce the damage done to cells by lack of oxygen in the blood.

We are asked to write a rate law for the metabolism of alcohol in the human body, a first-order process.
Using this information, we can prepare a plot of [ethanol] vs. time.
Analyze
A zero-order process has a rate law that does not include the concentration of the reactants. Since the rate
of reaction does not depend on the concentration, the metabolism will proceed at a constant rate under
given conditions.
Solve
The rate law for this process is
Rate = k
The plot of [ethanol] vs. time will proceed with a linear rate, reaching [ethanol] = 0 in two half lives:
Think About It
If the metabolism of ethanol was a first-order or second-order process, the rate of reaction would decrease
as the reaction proceeded.

In the case where ratereverse  rateforward we are to consider whether the method to determine the rate law
(initial concentrations and initial rates) would work at other times, not just at the start of the reaction. If so,
we are to specify which concentrations might be used to determine the rate law.
Analyze
The method that uses initial rates and concentrations to determine the rate law is under the condition where
no reverse reaction is occurring.
124 | Chapter 13
Solve
Yes, we could use this method at other times, not just t = 0, to determine the rate law if the rate of the
reverse reaction is much slower than the forward reaction as long as [products]  [reactants] at the time so
that no appreciable reverse reaction is occurring.
Think About It
We will see in Chapter 15 that when the rate of the reverse reaction equals the rate of the forward reaction,
the reaction is at equilibrium.

Given a statement relating reaction rate and the rate constant directly to the number of collisions occurring
in a reaction and the concentrations of the reactants, we are to determine what is incorrect about the
statement.
Analyze
The rate-law expression for a reaction describes the relationship between the concentration of reactants in
the reaction and the rate of the reaction. The rate constant in the rate law (k) relates the rate of the reaction
to the concentration of the reactants in a chemical reaction.
Solve
In the statement it is true that the reaction rate depends on the concentration of the reactants, as stated
explicitly by the rate-law expression. The reaction rate is also dependent on the number of collisions of the
reactants, since more frequent collisions (which can be accomplished by increasing the
reactant concentrations) will increase the reaction rate. However, the rate constant is not dependent on
either the concentrations or the number of collisions of the reactants. The value of k is unique to a reaction
and changes only with temperature or the use of a catalyst.
Think About It
The Arrhenius equation
k = Ae- Ea /RT
shows that k is dependent on the frequency factor, A; the activation energy, Ea; and the temperature, T.

We are asked why a mechanism cannot include an elementary step with a molecularity of zero.
Analyze
The molecularity of a reaction describes the number of molecules colliding in an elementary step.
Solve
An elementary step with a molecularity of zero would have no molecules colliding, so no reaction would
occur!
Think About It
A reaction may still have an order of zero with respect to a reactant if the reactant is not present in the
slowest elementary step.

Given the experimental rate data, we are asked to determine the rate law and rate constant for the reaction
between the chlorate and permanganate ions in the presence of acid.
Analyze
Holding the other concentrations constant, we may compare the ratio of rates of reaction for two
experiments to the increase in concentration of the reagent being varied. Raising the ratio of concentrations
of the species being changed to common orders of reaction (0, 1, 2, and ½), we may determine which order
is that reactant. To determine the order in H+, we will examine experiments 1 and 4; to determine the order
in ClO3−, we will examine experiments 1 and 3; to determine the order in MnO 4−, we will examine
experiments 1 and 2. Combining these individual reaction orders, we may determine the rate law for the
reaction. The rate constant may be obtained by substituting in experimental data from one of the listed
experiments.
Solve
The rate dependence on H+ is
7.4´ 10- 3
Rate ratio = = 1.4
5.2´ 10- 3
The concentration of H+ doubles from experiment 1 to experiment 4, while the other concentrations remain
the same. The order of the reaction with respect to H + is ½:
(2)1/2 = 1.4
The rate dependence on ClO3− is
0.30
Rate ratio = = 3.0
0.10
The concentration of ClO3− triples from experiment 1 to experiment 3, while the other concentrations
remain the same. The order of the reaction with respect to ClO 3− is 1:
(3)1 = 3
The rate dependence on MnO4− is
3.3´ 10- 2
Rate ratio = = 6.3
5.2´ 10- 3
The concentration of MnO4− increases by a factor of 2.5 from experiment 1 to experiment 2, while the other
concentrations remain the same. The order of the reaction with respect to MnO 4− is 2:
(2.5)2 = 6.3
Combining these reaction orders, the rate law is
Rate = k[H+]1/2[ClO3−][MnO4−]2
Using data from experiment 1, the rate constant is
5.2  10−3 M/s = k(0.10 M )1/2(0.10)(0.10)2
k = 16 M −2.5 s−1
Think About It
Noninteger reaction orders such as that observed for H + here are less common than integer reaction orders.
Note the effect this has on the overall reaction order (3.5) and the units of the rate constant
(M −2.5 s−1).
126 | Chapter 13

In the reaction of NO with Cl2, the rate of reaction was measured for various concentrations of both
reactants. From the data we can determine the rate law and calculate the rate constant k, which will allow us
to determine the initial rate of reaction in experiment 4.
Analyze
reactant, we can write the rate-law expression. To calculate the rate constant for the reaction, we rearrange
the rate law to solve for k and use the data from any of the experiments. Finally, we can calculate the rate of
the reaction for two different concentrations of the reactants by substituting those concentrations and the
calculated value of k into the rate-law expression.
Solve
Using experiments 1 and 2, we find that the order of the reaction with respect to Cl 2 is 2:
æ öx
rate 2 çç[Cl2 ]0,2 ÷
÷
=ç ÷
rate1 ççè[Cl2 ]0,1 ÷
÷
ø
5.70 M /s æ0.30 M ÷ öx
= çç ÷
0.63 M /s çè 0.10 M ÷
ø
x
9.0 = 3.0
x= 2
Using experiments 1 and 3, we find that the order of the reaction with respect to NO is 1:
æ öx
rate3 çç[NO ]0,3 ÷÷
=ç ÷
rate1 ççè[NO ]0,1 ÷
÷
ø
2.58 M /s æ0.80 M ÷ öx
= çç ÷
0.63 M /s çè 0.20 M ÷
ø
x
4.1 = 4.0
x= 1
This gives a rate law for the reaction of

Rate = k[NO][Cl2]2
Using experiment 1, we can calculate k:
2
0.63 M ×s- 1 = k (0.20 M )(0.10 M )
k = 315 M - 2 ×s- 1
Using the calculated value of k and the [NO]0 and [Cl2]0 for experiment 4, we calculate the rate for
experiment 4:
Rate = 315 M −2 s−1  0.40 M  (0.20 M ) 2
= 5.0 M/s
Think About It

For the reaction of NO with O3 to produce NO2 and O2, we can use the information that the reaction is first
order in both NO and O3 along with the values of the rate constants at two different temperatures to
determine whether the reaction occurs in a single or many steps and to calculate the activation energy, the
rate of the reaction at different concentrations of the reactants, and the rate constants at two other
temperatures.
Analyze
To answer the questions, we need to use the Arrhenius equation
Ea
ln k = - + ln A
RT
and the rate-law expression, which states that the reaction is first order in both NO and O 3:
Rate = k[NO][O3]
Solve
(a) Because the rate law where the reaction is first order in both NO and O 3 is consistent with that in
which the reaction would occur in a single step, this reaction might indeed occur in a single step.
(b) We can calculate the activation energy for the reaction by comparing the rate constant at the two
temperatures:
Ea æ
çç 1 ÷
ö
ln k298 K = - ÷+ ln A
R çè 298 K ÷
ø
Ea æ
çç 1 ÷
ö
ln k348 K = -
ç ÷
÷+ ln A
R è 348 K ø
Subtracting ln k at 25C from ln k at 75C gives

æk ö E æ 1 1 ö÷
ln k348 K - ln k298 K = ln çç 348 K ÷ ÷
÷ = - a çç - ÷
çè k298 K ø R çè 348 K 298 K ø÷
æ3000 M - 1 s- 1 ö÷ Ea æ 1 1 ö
ln ççç ÷= - ç
- 1ç
- ÷
÷
çè 80 M - 1 s- 1 ø÷
÷ ç ÷
8.314 J ×mol ×K 348 K 298 K ø
- 1
è
Ea = 6.25´ 104 J/mol or 62.5 kJ/mol
(c) We can use the rate-law expression to calculate the rate of the reaction at 25C when [NO] = 3  10−6 M
and [O3] = 5  10−9 M. We are given in the statement of the problem that k at 25C is 80 M −1 s−1.
Rate = 80 M −1 s−1  (3  10−6 M )  (5  10−9 M ) = 1.2  10−12 M/s
(d) To use the Arrhenius equation to calculate the values of k at 10C and 35C, we have to first determine
the value of the frequency factor A. To do this we can use the value for Ea and k for 25C:
128 | Chapter 13
6.25´ 104 J/mol æ ö

ç 1 ÷
ln (80 M - 1 s- 1 ) = - - 1ç ÷
÷+ ln A
ç
8.314 J ×mol ×K è 298 K ø
- 1
ln A = 29.608
A = 7.22´ 1012
So the value of k at 10C (283 K) is

6.25´ 104 J/mol æ ö
ç 1 ÷
ln k = - - 1ç ÷
÷+ ln (7.22´ 1012 )
ç
8.314 J ×mol ×K è 283 K ø
- 1
ln k = 3.045
k = 21 M - 1 s- 1
The value of k at 35C (308 K) is

6.25´ 104 J/mol æ ö
ç 1 ÷
ln k = - - 1ç ÷
÷+ ln (7.22´ 1012 )
ç
8.314 J ×mol ×K è 308 K ø
- 1
ln k = 5.20
k = 1. 8´ 102 M - 1 s- 1
Think About It
The values of k at 10C and 35C calculated above make sense because they are a little lower and a little
higher, respectively, than the value of k at 25C. Also, an Arrhenius plot using the two k values at 25C and
75C could be used to determine the activation energy and the frequency factor values in this problem.

Given the balanced reaction between NH3 and HNO2, we are asked to write the rate law and determine the
units of the rate constant, compare the rate law to an alternate expression that includes the species NH 4+ and
NO2−, calculate the enthalpy of the overall reaction, and draw the reaction-energy profile for the reaction
occurring by a two-step mechanism.
Analyze
This problem puts together many of the concepts in this chapter (writing rate laws from experimental
results, drawing a reaction profile for a multistep reaction) along with calculation of the enthalpy of a
reaction from Chapter 5.
Solve
(a) Because the reaction is first order in [NH3] and second order in [HNO2], the rate law is Rate =
k[NH3][HNO2]2. If the rate is in units of M/s, then the units of k are
M /s
2
= M - 2 ×s- 1
(M )(M )
(b) Yes, the expression is equivalent to the rate law in part (a).
If the formation of NH4+ and NO2− is an equilibrium step, then
NH3 + HNO2 = NH4+ + NO2−
k1[NH3][HNO2] = k−1[NH4+][NO2−]
Solving for [NH3][HNO2] gives
k- 1 é
k1 = [NH3 ][HNO 2 ]= NH 4+ ùéNO - ù
k1 êë úê
ûë 2 úû
Substituting into the rate equation in part (a) gives

k- 1 é
Rate = k NH 4+ ùéNO - ù[HNO 2 ]
k1 êë úê
ûë 2 ú û
= k éêNH 4+ ùé
úêNO - ù[HNO 2 ]
ë ûë 2 ú û

(c) Η rxn = [(1 mol N 2 ´ 0.0 kJ/mol) + (2 mol H 2O´ - 285.8 kJ/mol)]
- [(1 mol NH3 ´ - 46.1 kJ/mol) + (1 mol HNO2 ´ - 43.1 kJ/mol)]
= - 482.4 kJ
(d)
Think About It
From the reaction energy diagram, we see that the second step is the rate-limiting step.

For the second-order decomposition of PAN, we are to calculate k for the reaction given t1/ 2 , determine the
rate of the reaction when the partial pressure of PAN is 10.5 torr, and draw a plot of PPAN versus time from
0 to 200 h.
Analyze
This problem puts together many of the concepts in this chapter (using t1/ 2 to calculate k, calculating the
rate of a reaction from the rate law, and plotting change in the concentration, here partial pressure, of a
reactant over time).
Solve
(a) From t1/ 2 we calculate k for this second-order reaction, where PPAN = 10.5 torr:
1 1 1
t1/ 2 = or k= = = 9.52´ 10- 4 torr - 1 ×h - 1
k [A ]0 t1/ 2 [A ]0 100 h ´ 10.5 torr
(b) For a second-order reaction, the rate law is

2 2
Rate = k [A ]0 = k (PPAN )
9.52´ 10- 4 2
= ´ (10.5 torr ) = 0.105 torr/h
torr ×h
(c)
130 | Chapter 13
Think About It
From the plot in part (c), we may determine the instantaneous rate of the reaction at any time by
determining the slope of the tangent line at that point.

For the reaction of NO with ONOO−, we are to use the provided data to determine the rate law and rate
constant for the reaction. We are also to draw the Lewis structure of peroxynitrite ion with resonance

forms, formal charges, and an indication of which is the preferred form. We must also estimate H rxn
using the preferred resonance structure.
Analyze
To determine the rate law, we can compare the effects of changing the concentrations of NO and ONOO −
on the rate of the reaction. After drawing the resonance forms for ONOO− we can determine which is the

preferred structure by assigning formal charges to the atoms in each resonance form. The H rxn may be
estimated by bond energies using

H rxn = å H bond breaking + å H bond forming
Solve
(a) For the order of reaction with respect to ONOO− we can compare experiments 1 and 2:
æéONOO- ù ÷ öx
ç
rate 2 ç ëê ú
û0,2 ÷
=ç ÷
÷
rate1 ççç éêONOO- ùú ÷ ÷
èë û0,1 ÷
ø
1.02´ 10- 11 M /s æ öx
çç 0.625´ 10 M ÷
- 4
= ÷
2.03´ 10- 11 M /s ççè 1.25´ 10- 4 M ÷
÷
ø
0.502 = 0.500 x
x= 1
Notice that there are not two experiments in the data table for which the concentration of ONOO − stays
the same. For the order of reaction with respect to NO, we can compare experiments 2 and 3 as long as we
take into account the knowledge that the reaction is first order in ONOO −. Between these two experiments,
we see that as the ONOO− concentration is quadrupled, we would expect that the rate would be quadrupled.
However, the rate of the reaction, when the NO concentration is halved simultaneously with the
quadrupling of the rate of the reaction, doubles:
rate3 æ ö
2.03´ 10- 11 M /s ÷
= ççç ÷
÷ = 1.99
rate2 çè1.02´ 10 M /s ÷
- 11
ø
Because the [ONOO−] = 4 (which would quadruple the rate of the reaction), the [NO] must affect the
rate by 1.99/4 = 0.498. Therefore,
æ0.625´ 10- 4 M ÷ öx
ç
0.498 = çç ÷
çè 1.25´ 10- 4 M ÷
÷
ø
0.498 = 0.500 x
x= 1
The rate law for this reaction is Rate = k[NO][ONOO−].
We can use any experiment to calculate the value of k. Using the data from experiment 1:
2.03  10−11 M/s = k  (1.25  10−4 M )  (1.25  10−4 M )
k = 1.30  10−3 M −1 s−1
(b)
(c)
Bonds broken = O—O (146 kJ/mol)

Bonds formed = N—O (201 kJ/mol)
Hrxn = [1 mol  146 kJ/mol] + [1 mol  (−201 kJ/mol)] = −55 kJ
Think About It
To solve this problem you had to draw on several concepts you have learned so far in this course. You had
to review not only how to write a rate law given kinetic data, but also how to draw resonance structures and
how bond energies might be used to estimate the enthalpy of a reaction.

Using the raw data obtained for four experiments in which the concentrations of NH 2 and NO were varied,
we are to write the rate law and determine the value of k for the reaction between NH2 and NO at 1200 K.
Analyze
To determine the rate law, we can compare the effects of changing the concentrations of NH 2 and NO on
the rate of the reaction. Once we have determined the order of the reaction with respect to each reactant, we
can write the rate-law expression and use any of the experiments to calculate the value of the rate
constant, k.
Solve
(a) For the order of the reaction with respect to NH 2, we can use the data from experiments 1 and 2:
Solution Manual for Chemistry The Science in Context, 5th edition, Thomas R Gilbert, Rein V
132 | Chapter 13
æ öx
rate 2 çç[NH 2 ]0,2 ÷
÷
=ç ÷
rate1 ççè[NH 2 ]0,1 ÷
÷
ø
0.24 M /s æ öx
2.00´ 10- 5 M ÷
ç
=ç ÷
0.12 M /s ççè1.00´ 10- 5 M ÷
÷
ø
2.0 = 2.00 x
x= 1
For the order of the reaction with respect to NO, we can use the data from experiments 2 and 3:
æ öx
rate3 çç[NO ]0,3 ÷ ÷
=ç ÷
rate 2 ççè[NO ]0,2 ÷
÷
ø
x
0.36 M /s æ 1.50´ 10- 5 M ö÷
= ççç ÷
0.24 M /s çè1.00´ 10- 5 M ø÷ ÷
1.5 = 1.50 x
x= 1
The rate-law expression is rate = k[NH2][NO].

(b) Using experiment 1 to calculate the value of k,
0.12 M/s = k  (1.00  10−5 M )  (1.00  10−5 M )
k = 1.2  109 M −1 s−1
Think About It
Any of the experiments listed in the data table would give us the same value of k in the calculation in
part (b).
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Solution Manual for Chemistry The Science in

Context, 5th edition, Thomas R Gilbert, Rein V Kirss,

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CHAPTER 13 | Chemical Kinetics: Reactions in the Atmosphere

13.1. Collect and Organize

13.2. Collect and Organize

13.3. Collect and Organize

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13.4. Collect and Organize

13.5. Collect and Organize

13.6. Collect and Organize

13.7. Collect and Organize

13.8. Collect and Organize

13.9. Collect and Organize

13.10. Collect and Organize

13.11. Collect and Organize

13.12. Collect and Organize

13.13. Collect and Organize

13.14. Collect and Organize

13.15. Collect and Organize

13.16. Collect and Organize

13.17. Collect and Organize

13.18. Collect and Organize

13.19. Collect and Organize

13.20. Collect and Organize

13.21. Collect and Organize

13.22. Collect and Organize

13.23. Collect and Organize

13.24. Collect and Organize

13.25. Collect and Organize

13.26. Collect and Organize

13.27. Collect and Organize

1 [NO ] [N 2 ] [O 2 ]

13.28. Collect and Organize

(b) The relationship between [CO] and [CO2] is

13.29. Collect and Organize

1 [A ] 1 [B] 1 [C ] 1 [D ]

13.30. Collect and Organize

13.31. Collect and Organize

13.32. Collect and Organize

13.33. Collect and Organize

13.34. Collect and Organize

13.35. Collect and Organize

13.36. Collect and Organize

= - 2´ (- 2.2´ 105 mM /min )

= 4.4´ 105 mM /min

1  [NO 2 ] 1  [NO3 ]  [NO 2 ]  [NO3 ]

13.37. Collect and Organize

 [O3 ] [O3 ]f - [O3 ]i

 [O3 ] (9.93´ 10 - 1.13´ 10 )M

- = = 1.4´ 10- 5 M /ms

 [O3 ] (8.15´ 10 - 8.70´ 10 )M

- = = 5.50´ 10- 6 M /ms

13.38. Collect and Organize

 [N 2O5 ] [N 2O5 ]f - [N 2O5 ]i

 [N 2O5 ] (1.357 ´ 10 - 1.500´ 10 )molecules/cm

- = = 9.86´ 1010 molecules/(cm3 ×s)